Aminomethylene derivatives and ultraviolet absorbent comprising thereof

ABSTRACT

The present invention provides an aminomethylene derivative represented by general formula (I): ##STR1## wherein A is a cyclic oxo group selected from the group consisting of following general formulae (a), (b), (c), (d) and (e): ##STR2## wherein R 1 , R 2 , R 3 , R 4  and R 5  each independently represent H, an alkyl group or the like; R 6 , R 7  and R 8  each independently represent an alkyl group or the like; R 1  and R 2  or R 7  and R 8  may combine with each other to form a tetramethylene group or the like; R represents an alkyl group optionally containing OH or O; and n is an integer of 0 to 4, a process for the same, and the use thereof. The derivatives have an excellent ultraviolet absorption ability and a high optical stability.

This application is a 371 of PCT/JP97/03536, filed Oct. 3, 1997.

TECHNICAL FIELD

The present invention relates to aminomethylene derivatives havingexcellent ultraviolet absorptivity and high light stability, andultraviolet absorbent, cosmetic materials and weatherproofing polymercomposition comprising thereof, and methods for producing abovedescribed aminomethylene derivatives.

PRIOR ART

It has been known that organic substances, especially polymer compounds,are subjected to yellowing, discoloration, cracking or embrittlement bythe action of ultraviolet rays. Meanwhile, ultraviolet rays that reachto the ground surface consist mostly of UV-B (280 to 320 nm) and UV-A(320 to 400 nm). Among them, ultraviolet rays of the UV-A range, whenmore than a certain amount of them is applied to the skin, cause rash orblisters and are also considered to causes lowering of elasticity orbrowning of the skin. In order to prevent such changes of the skincaused by ultraviolet rays of the UV-A range, so called sunscreencosmetics which contain ultraviolet absorbent are known. As knownultraviolet absorbents that have been used there are benzophenonederivatives including 4-phenylbenzophenone and2-hydroxy-4-methoxybenzophenone-5-sulfonic acid, dibenzoylmethanederivatives including 4-tert-butyl-4'-methoxydibenzoylmethane, andbenzotriazole derivatives including2-(2-hydroxy-5-methoxyphenyl)benzotriazole.

Above described conventional synthetic compounds which are used asultraviolet absorbent for UV-A in organic substances, especially inpolymer compounds, have defect that they react with metal ions and causecoloring. Further, since ultraviolet absorbents themselves are coloredin general, the amount of use is restricted. On the other hand,conventionally known synthetic compounds used as UV-A absorbents whichare usually added to cosmetic materials and others, have limits on theamount can be used because of their irritativeness to the skin, andtherefore, they cannot be used at the sufficient amount required forprotecting the skin from sunburn and can provide only smaller UV-Aprotection effect. Therefore, development of a synthetic compound thatabsorbs ultraviolet rays of the UV-A range and shows much highabsorption, in other words has higher molecular absorptivity, has beenexpected.

OBJECT OF THE INVENTION

The primary object of the present invention is to provide a novelcompound showing much high absorption, in other words has highermolecular absorptivity, and a method for producing the same.

The second object of the present invention is to provide a novelultraviolet absorbent through utilizing above described ultravioletabsorptivity, a cosmetic material and a weatherproofing organic polymercomposition including thereof.

DISCLOSURE OF THE INVENTION

The first aspect of the present invention relates to an aminomethylenederivative represented by general formula (I): ##STR3## in which A is acyclic oxo group selected from the group consisting of following generalformulae (a), (b), (c), (d) and (e), ##STR4## wherein R¹, R², R³, R⁴ andR⁵ each independently are groups selected from the group consisting of ahydrogen atom, linear or branched, saturated or unsaturated alkylgroups, cycloalkyl groups, aralkyl groups and aryl groups, R⁶ is a groupselected from the group consisting of linear or branched, saturated orunsaturated alkyl groups, cycloalkyl groups, aralkyl groups, arylgroups, a hydroxyl group, alkoxy groups, alkoxycarbonyl groups, acylgroups, an amino group, acylamino groups, alkylamino groups,dialkylamino groups, arylamino groups and halogens, R⁷ and R⁸ eachindependently are groups selected from the group consisting of linear orbranched, saturated or unsaturated alkyl groups, cycloalkyl groups,aralkyl groups and aryl groups, further R¹ and R² or R⁷ and R⁸ can,together, form a tetramethylene group, pentamethylene group orhexamethylene group, and R is a group selected from the group consistingof linear or branched, saturated or unsaturated alkyl groups, aralkylgroups, aryl groups, cycloalkyl groups, alkyl groups containing hydroxylgroup, alkoxycarbonylalkylene groups and alkyl groups containing oxygenatom, and n is an integer of 0 to 4 wherein when n is 2 or more, each ofplural R⁶ s can be different groups within above described groups.

The second aspect of the present invention relates to an ultravioletabsorbent containing said aminomethylene derivative.

The third aspect of the present invention relates to a cosmetic materialcontaining said aminomethylene derivative.

The fourth aspect of the present invention relates to a weatherproofingorganic polymer composition containing said aminomethylene derivative.

The fifth aspect of the present invention relates to a method forproducing an aminomethylene derivative represented by following generalformula (I): ##STR5## wherein A is a cyclic oxo group selected from thegroup consisting of following general formulae (a), (b), (c), (d) and(e): ##STR6## wherein R¹, R², R³, R⁴ and R⁵ each independently aregroups selected from the group consisting of a hydrogen atom, linear orbranched, saturated or unsaturated alkyl groups, cycloalkyl groups,aralkyl groups and aryl groups, R⁶ is a group selected from the groupconsisting of linear or branched, saturated or unsaturated alkyl groups,cycloalkyl groups, aralkyl groups, aryl groups, a hydroxyl group, alkoxygroups, alkoxycarbonyl groups, acyl groups, an amino group, acylaminogroups, alkylamino groups, dialkylamino groups, arylamino groups andhalogens, R⁷ and R⁸ each independently are groups selected from thegroup consisting of linear or branched, saturated or unsaturated alkylgroups, cycloalkyl groups, aralkyl groups and aryl groups, further R¹and R² or R⁷ and R⁸ can, together, form a tetramethylene group,pentamethylene group or hexamethylene group, and R is a group selectedfrom the group consisting of linear or branched, saturated orunsaturated alkyl groups, aralkyl groups, aryl groups, cycloalkylgroups, alkyl groups containing hydroxyl group, alkoxycarbonylalkylenegroups and alkyl groups containing oxygen atom, and n is an integer of 0to 4 wherein when n is 2 or more, each of plural R⁶ s can be differentgroups within above described groups, characterised in that a cyclic oxocompound represented by the general formula (II):

    A'                                                         (II)

wherein A' is a compound selected from the group consisting of followinggeneral formulae (a'), (b'), (c'), (d') and (e'): ##STR7## wherein R¹,R², R³, R⁴ and R⁵ each independently are groups selected from the groupconsisting of an hydrogen atom, linear or branched, saturated orunsaturated alkyl groups, cycloalkyl groups, aralkyl groups and arylgroups, R⁶ is a group selected from the group consisting of linear orbranched, saturated or unsaturated alkyl groups, cycloalkyl groups,aralkyl groups, aryl groups, a hydroxyl group, alkoxy groups,alkoxycarbonyl groups, acyl groups, an amino group, acylamino groups,alkylamino groups, dialkylamino groups, arylamino groups and halogens,R⁷ and R⁸ each independently are groups selected from the groupconsisting of linear or branched, saturated or unsaturated alkyl groups,cycloalkyl groups, aralkyl groups and aryl groups, further R¹ and R² orR⁷ and R⁸ can, together form a tetramethylene group, pentamethylenegroup or hexamethylene group, and n is an integer of 0 to 4 wherein whenn is 2 or more, each of plural R⁶ s can be different groups within abovedescribed groups, is allowed to react with an N-formylamino benzoatederivative represented by general formula (III): ##STR8## wherein R is agroup selected from the group consisting of linear or branched,saturated or unsaturated alkyl groups, cycloalkyl groups, aralkylgroups, aryl groups, alkyl groups containing hydroxyl group,alkoxycarbonylalkylene groups and alkyl groups containing oxygen atom,in organic solvent and in the presence of an acid catalyst.

Regarding to R¹, R², R³, R⁴ and R⁵, examples of linear or branched,saturated or unsaturated alkyl groups include methyl, ethyl, propyl,isopropyl, butyl, isobutyl, or allyl groups but those having 1 to 8carbon atoms are preferable. Examples of above described cycloalkylgroups include cyclopentyl and cyclohexyl. Examples of above describedaralkyl groups include those of which one hydrogen of said alkyl groupsis substituted by a phenyl group, such as phenylethyl and phenylpropylgroups. Examples of above described aryl groups include a phenyl groupand phenyl groups substituted by methyl, methoxy, ethoxy,methoxycarbonyl, ethoxycarbonyl, halogen, acetyl, cyano group or thelike.

Regarding to R⁶, examples of above described linear or branched,saturated or unsaturated alkyl groups include methyl, ethyl, n-propyl,isopropyl, n-butyl, isobutyl, t-butyl, allyl, but those having 1 to 8carbon atoms are preferable. Examples of above described cycloalkylgroups include cyclopentyl and cyclohexyl groups. Examples of abovedescribed aralkyl groups include those of which one hydrogen of saidalkyl groups is substituted by a phenyl group, such as benzyl,phenylethyl and phenylpropyl groups. Examples of above described arylgroups include a phenyl group and phenyl groups substituted by alkylgroups such as methyl and ethyl, alkoxyl groups such as methoxy andethoxy, alkoxycarbonyl groups such as methoxycarbonyl andethoxycarbonyl, or other substituent such as a halogen, acetyl andcyano.

Examples of above described alkoxy groups include methoxy group, ethoxygroup, n-propoxy group, isopropoxy group and n-butoxy group. Examples ofabove described alkoxycarbonyl groups include methoxycarbonyl group andethoxycarbonyl group. Examples of above described acyl groups includeacetyl group, n-propionyl group and isopropionyl group. Examples ofabove described acylamino groups include acetylamino group andn-propionylamino group. Examples of above described alkylamino groupsinclude amino groups having above described alkyl groups, such asmethylamino group and ethylamino group. Examples of above describeddialkylamino groups include dimethylamino group and diethylamino group.Examples of above described arylamino groups include amino groups havingabove described aryl groups, such as phenylamino group, tolylaminogroup, anisylamino group.

Regarding R⁷ and R⁸, examples of above described linear or branched,saturated or unsaturated alkyl groups include methyl, ethyl, n-propyl,isopropyl, n-butyl, isobutyl and allyl groups, but those having 1 to 8carbon atoms are preferable. Examples of above described cycloalkylgroups include cyclopentyl and cyclohexyl groups. Examples of abovedescribed aralkyl groups include those of which one hydrogen of saidalkyl groups is substituted by a phenyl group, such as phenylethyl andphenylpropyl groups. Examples of above described aryl groups include aphenyl group and phenyl groups substituted by methyl, methoxy, ethoxy,methoxycarbonyl, ethoxycarbonyl, halogen, acetyl, cyano or the like.

Further R¹ and R² or R⁷ and R⁸ can, together form a tetramethylenegroup, pentamethylene group or hexamethylene group.

Regarding R, examples of above described linear or branched, saturatedor unsaturated alkyl groups include methyl group, ethyl group, n-propylgroup, isopropyl group, n-butyl group, isobutyl group, sec-butyl group,tert-butyl group, n-pentyl group, n-hexyl group, n-heptyl group,2-ethylhexyl group, n-octyl group, n-nonyl group, isononyl group,n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group,iso-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecylgroup, n-heptadecyl group, n-octadecyl group, n-eicosyl group, allylgroup and propene group, but those having carbon atoms of 1 to 20 arepreferable. Longer alkyl groups also can be used, in that case,synthesis is performed using oxo process or the Ziegler process.Examples of above described aralkyl groups, cycloalkyl groups and arylgroups can be the same with the examples described regarding to R¹ andR². Examples of above described alkyl group having hydroxyl groupincludes methylol group and ethylol group. Examples of above describedalkoxycarbonylalkylene groups include methoxycarbonylmethyl group,ethoxycarbonylmethyl group and 2-ethylhexyloxylcarbonylmethyl group.Examples of above described alkyl groups having oxygen atom includemethoxyethyl group, ethoxyethyl group and methoxyethyloxy group.

Above described reaction is generally performed at a temperature rangeof 10 to 60° C., preferably 30 to 50° C., and examples of organicsolvent used for the reaction can be any solvent that dissolvescompounds represented by the general formula (I) and (II), respectivelyand include aromatic hydrocarbons and halogenated alkyls, such astoluene, xylene, dichloroethylene and chloroform.

Examples of above described acid catalyst include phosphoruspentachloride, phosphorus trichloride, phosphorus oxychloride, thionylchloride and sulfuryl chloride.

Organic materials stabilized by the compound represented by the generalformula (I), for example cosmetic materials and polymer materials, canfurther include conventionally used additives such as an antioxidant,light stabilizing agent, metal deactivator and peroxide scavenger.

Said organic materials may be natural or synthetic polymers, for examplecellulose, CMC, natural rubbers, synthetic rubbers such as SBR, NBR orthe like, polyolefins such as polyethylene, polypropylene or the like,synthetic resins such as polyester, polyamide, polyurethane, polyvinylchloride or the like, and so on.

Of the aminomethylene derivatives represented by the general formula (I)used in the present invention, concrete examples ofaminomethylenecyclohexane derivatives in which A in the formula (I) is(a), represented by the formula (Ia): ##STR9## wherein R¹, R² and R areas defined above, include following compounds:

2-(4-ethoxycarbonylphenylamino)-methylene-1,3-cyclohexadione;

2-(4-isopropoxycarbonylphenylamino)-methylene-1,3-cyclohexadione;

2-(4-isobutoxycarbonylphenylamino)-methylene-1,3-cyclohexadione;

2-(4-sec-butoxycarbonylphenylamino)-methylene-1,3-cyclohexadione;

2-(4-tert-butoxycarbonylphenylamino)-methylene-1,3-cyclohexadione;

2-(4-n-pentyloxycarbonylphenylamino)-methylene-1,3-cyclohexadione;

2-(4-n-hexyloxycarbonylphenylamino)-methylene-1,3-cyclohexadione;

2-(4-n-heptyloxycarbonylphenylamino)-methylene-1,3-cyclohexadione;

2-(4-n-nonyloxycarbonylphenylamino)-methylene-1,3-cyclohexadione;

2-(4-n-decyloxycarbonylphenylamino)-methylene-1,3-cyclohexadione;

2-(4-n-undecyloxycarbonylphenylamino)-methylene-1,3-cyclohexadione;

2-(4-n-dodecyloxycarbonylphenylamino)-methylene-1,3-cyclohexadione;

2-(4-n-tridecyloxycarbonylphenylamino)-methylene-1,3-cyclohexadione;

2-(4-n-tetradecyloxycarbonylphenylamino)-methylene-1,3-cyclohexadione;

2-(4-n-pentadecyloxycarbonylphenylamino)-methylene-1,3-cyclohexadione;

2-(4-n-hexadecyloxycarbonylphenylamino)-methylene-1,3-cyclohexadione;

2-(4-n-heptadecyloxycarbonylphenylamino)-methylene-1,3-cyclohexadione;

5,5-dimethyl-2-(4-ethoxycarbonylphenylamino)-methylene-1,3-cyclohexadione;

5,5-dimethyl-2-(4-isopropoxycarbonylphenylamino)-methylene-1,3-cyclohexadione;

5,5-dimethyl-2-(4-isobutoxycarbonylphenylamino)-methylene-1,3-cyclohexadione;

5,5-dimethyl-2-(4-sec-butoxycarbonylphenylamino)-methylene-1,3-cyclohexadione;

5,5-dimethyl-2-(4-tert-butoxycarbonylphenylamino)-methylene-1,3-cyclohexadione;

5,5-dimethyl-2-(4-n-pentyloxycarbonylphenylamino)-methylene-1,3-cyclohexadione;

5,5-dimethyl-2-(4-n-hexyloxycarbonylphenylamino)-methylene-1,3-cyclohexadione;

5,5-dimethyl-2-(4-n-heptyloxycarbonylphenylamino)-methylene-1,3-cyclohexadione;

5,5-dimethyl-2-(4-n-nonyloxycarbonylphenylamino)-methylene-1,3-cyclohexadione;

5,5-dimethyl-2-(4-n-decyloxycarbonylphenylamino)-methylene-1,3-cyclohexadione;

5,5-dimethyl-2-(4-n-undecyloxycarbonylphenylamino)-methylene-1,3-cyclohexadione;

5,5-dimethyl-2-(4-n-dodecyloxycarbonylphenylamino)-methylene-1,3-cyclohexadione;

5,5-dimethyl-2-(4-n-tridecyloxycarbonylphenylamino)-methylene-1,3-cyclohexadione;

5,5-dimethyl-2-(4-n-tetradecyloxycarbonylphenylamino)-methylene-1,3-cyclohexadione;

5,5-dimethyl-2-(4-n-pentadecyloxycarbonylphenylamino)-methylene-1,3-cyclohexadione;

5,5-dimethyl-2-(4-n-hexadecyloxycarbonylphenylamino)-methylene-1,3-cyclohexadione;

5,5-dimethyl-2-(4-n-heptadecyloxycarbonylphenylamino)-methylene-1,3-cyclohexadione;

5,5-diethyl-2-(4-methoxycarbonylphenylamino)-methylene-1,3-cyclohexadione;

5,5-diethyl-2-(4-ethoxycarbonylphenylamino)-methylene-1,3-cyclohexadione;

5,5-diethyl-2-(4-n-propoxycarbonylphenylamino)-methylene-1,3-cyclohexadione;

5,5-diethyl-2-(4-isopropoxycarbonylphenylamino)-methylene-1,3-cyclohexadione;

5,5-diethyl-2-(4-n-butoxycarbonylphenylamino)-methylene-1,3-cyclohexadione;

5,5-diethyl-2-(4-n-pentyloxycarbonylphenylamino)-methylene-1,3-cyclohexadione;

5,5-diethyl-2-(4-n-hexyloxycarbonylphenylamino)-methylene-1,3-cyclohexadione;

5,5-diethyl-2-(4-n-heptyloxycarbonylphenylamino)-methylene-1,3-cyclohexadione;

5,5-diethyl-2-[4-(2-ethylhexyloxycarbonylphenylamino)]-methylene-1,3-cyclohexadione;

5,5-diethyl-2-(4-n-octadecyloxycarbonylphenylamino)-methylene-1,3-cyclohexadione;

5,5-dimethyl-2-(4-methoxyethylcarbonylphenylamino)-methylene-1,3-cyclohexadione;

5,5-dimethyl-2-(4-ethoxyethylcarbonylphenylamino)-methylene-1,3-cyclohexadione;

5,5-dimethyl-2-(4-methoxycarbomethyloxycarbonylphenylamino)-methylene-1,3-cyclohexadione;

5,5-dimethyl-2-(4-ethoxycarbomethyloxycarbonylphenylamino)-methylene-1,3-cyclohexadione;

5,5-diethyl-2-(4-methoxyethylcarbonylphenylamino)-methylene-1,3-cyclohexadione;

5,5-diethyl-2-(4-ethoxyethylcarbonylphenylamino)-methylene-1,3-cyclohexadione;

5,5-diethyl-2-(4-methoxycarbomethyloxycarbonylphenylamino)-methylene-1,3-cyclohexadione;

5,5-diethyl-2-(4-ethoxycarbomethyloxycarbonylphenylamino)-methylene-1,3-cyclohexadione,and so on.

Of the aminomethylene derivatives represented by the general formula (I)used in the present invention, concrete examples of aminomethylenepyrone derivatives in which A in formula (I) is (b), represented by theformula (Ib): ##STR10## wherein R³ and R are as defined above, includefollowing compounds:6-methyl-3-(4-ethoxycarbonylphenylaminomethylene)-2H,3H,4H-pyrane-2,4-dione;

6-methyl-3-(4-isopropoxycarbonylphenylaminomethylene)-2H,3H,4H-pyrane-2,4-dione;

6-methyl-3-(4-isobutoxycarbonylphenylaminomethylene)-2H,3H,4H-pyrane-2,4-dione;

6-methyl-3-(4-sec-butoxycarbonylphenylaminomethylene)-2H,3H,4H-pyrane-2,4-dione;

6-methyl-3-(4-tert-butoxycarbonylphenylaminomethylene)-2H,3H,4H-pyrane-2,4-dione;

6-methyl-3-(4-n-pentyloxycarbonylphenylaminomethylene)-2H,3H,4H-pyrane-2,4-dione;

6-methyl-3-(4-n-hexyloxycarbonylphenylaminomethylene)-2H,3H,4H-pyrane-2,4-dione;

6-methyl-3-(4-n-heptyloxycarbonylphenylaminomethylene)-2H,3H,4H-pyrane-2,4-dione;

6-methyl-3-(4-n-nonyloxycarbonylphenylaminomethylene)-2H,3H,4H-pyrane-2,4-dione;

6-methyl-3-(4-n-decyloxycarbonylphenylaminomethylene)-2H,3H,4H-pyrane-2,4-dione;

6-methyl-3-(4-n-undecyloxycarbonylphenylaminomethylene)-2H,3H,4H-pyrane-2,4-dione;

6-methyl-3-(4-n-dodecyloxycarbonylphenylaminomethylene)-2H,3H,4H-pyrane-2,4-dione;

6-methyl-3-(4-n-tridecyloxycarbonylphenylaminomethylene)-2H,3H,4H-pyrane-2,4-dione;

6-methyl-3-(4-n-tetradecyloxycarbonylphenylaminomethylene)-2H,3H,4H-pyrane-2,4-dione;

6-methyl-3-(4-n-pentadecyloxycarbonylphenylaminomethylene)-2H,3H,4H-pyrane-2,4-dione;

6-methyl-3-(4-n-hexadecyloxycarbonylphenylaminomethylene)-2H,3H,4H-pyrane-2,4-dione;

6-methyl-3-(4-n-heptadecyloxycarbonylphenylaminomethylene)-2H,3H,4H-pyrane-2,4-dione;

6-ethyl-3-(4-methoxycarbonylphenylaminomethylene)-2H,3H,4H-pyrane-2,4-dione;

6-ethyl-3-(4-ethoxycarbonylphenylaminomethylene)-2H,3H,4H-pyrane-2,4-dione;

6-ethyl-3-(4-n-propoxycarbonylphenylaminomethylene)-2H,3H,4H-pyrane-2,4-dione;

6-ethyl-3-(4-isopropoxycarbonylphenylaminomethylene)-2H,3H,4H-pyrane-2,4-dione;

6-ethyl-3-(4-n-butoxycarbonylphenylaminomethylene)-2H,3H,4H-pyrane-2,4-dione;

6-ethyl-3-(4-n-pentyloxycarbonylphenylaminomethylene)-2H,3H,4H-pyrane-2,4-dione;

6-ethyl-3-(4-n-hexyloxycarbonylphenylaminomethylene)-2H,3H,4H-pyrane-2,4-dione;

6-ethyl-3-(4-n-heptyloxycarbonylphenylaminomethylene)-2H,3H,4H-pyrane-2,4-dione;

6-ethyl-3-[4-(2-ethylhexyloxycarbonylphenyl)aminomethylene]-2H,3H,4H-pyrane-2,4-dione;

6-ethyl-3-(4-n-octadecyloxycarbonylphenylaminomethylene)-2H,3H,4H-pyrane-2,4-dione;

6-methyl-3-(4-methoxylethylcarbonylphenylaminomethylene)-2H,3H,4H-pyrane-2,4-dione;

6-methyl-3-(4-ethoxyethylcarbonylphenylaminomethylene)-2H,3H,4H-pyrane-2,4-dione;

5-methyl-3-(4-methoxycarbonylmethyloxycarbonylphenylaminomethylene)-2H,3H,4H-pyrane-2,4-dione;

6-methyl-3-(4-ethoxycarbonylmethyloxycarbonylphenylaminomethylene)-2H,3H,4H-pyrane-2,4-dione;

6-ethyl-3-(4-methoxyethylcarbonylphenylaminomethylene)-2H,3H,4H-pyrane-2,4-dione;

6-ethyl-3-(4-ethoxyethylcarbonylphenylaminomethylene)-2H,3H,4H-pyrane-2,4-dione;

6-ethyl-3-(4-methoxycarbonylmethyloxycarbonylphenylaminomethylene)-2H,3H,4H-pyrane-2,4-dione;

6-ethyl-3-(4-ethoxycarbonylmethyloxycarbonylphenylaminomethylene)-2H,3H,4H-pyrane-2,4-dione,and so on.

Of the aminomethylene derivatives represented by the general formula (I)used in the present invention, concrete examples of aminomethylenebarbituric acid derivatives in which A in the formula (I) is (c),represented by the formula (Ic): ##STR11## wherein R⁴, R⁵ and R are asdefined above, include following compounds:

1,3-dimethyl-5-(4-ethoxycarbonylphenylamino)-methylene-barbituric acid;

1,3-dimethyl-5-(4-isopropoxycarbonylphenylamino)-methylene-barbituricacid;

1,3-dimethyl-5-(4-isobutoxycarbonylphenylamino)-methylene-barbituricacid;

1,3-dimethyl-5-(4-sec-butoxycarbonylphenylamino)-methylene-barbituricacid;

1,3-dimethyl-5-(4-tert-butoxycarbonylphenylamino)-methylene-barbituricacid;

1,3-dimethyl-5-(4-n-pentyloxycarbonylphenylamino)-methylene-barbituricacid;

1,3-dimethyl-5-(4-n-hexyloxycarbonylphenylamino)-methylene-barbituricacid;

1,3-dimethyl-5-(4-n-heptyloxycarbonylphenylamino)-methylene-barbituricacid;

1,3-dimethyl-5-(4-n-nonyloxycarbonylphenylamino)-methylene-barbituricacid;

1,3-dimethyl-5-(4-n-decyloxycarbonylphenylamino)-methylene-barbituricacid;

1,3-dimethyl-5-(4-n-undecyloxycarbonylphenylamino)-methylene-barbituricacid;

1,3-dimethyl-5-(4-n-dodecyloxycarbonylphenylamino)-methylene-barbituricacid;

1,3-dimethyl-5-(4-n-tridodecyloxycarbonylphenylamino)-methylene-barbituricacid;

1,3-dimethyl-5-(4-n-tetradodecyloxycarbonylphenylamino)methylene-barbituricacid;

1,3-dimethyl-5-(4-n-pentadecyloxycarbonylphenylamino)-methylene-barbituricacid;

1,3-dimethyl-5-(4-n-hexadecyloxycarbonylphenylamino)-methylene-barbituricacid;

1,3-dimethyl-5-(4-n-heptadecyloxycarbonylphenylamino)-methylene-barbituricacid;

1,3-diethyl-5-(4-methoxycarbonylphenylamino)-methylene-barbituric acid;

1,3-diethyl-5-(4-ethoxycarbonylphenylamino)-methylene-barbituric acid;

1,3-diethyl-5-(4-n-propoxycarbonylphenylamino)-methylene-barbituricacid;

1,3-diethyl-5-(4-isopropoxycarbonylphenylamino)-methylene-barbituricacid;

1,3-diethyl-5-(4-n-butoxycarbonylphenylamino)-methylene-barbituric acid;

1,3-diethyl-5-(4-n-pentyloxycarbonylphenylamino)-methylene-barbituricacid;

1,3-diethyl-5-(4-n-hexyloxycarbonylphenylamino)-methylene-barbituricacid;

1,3-diethyl-5-(4-n-heptyloxycarbonylphenylamino)-methylene-barbituricacid;

1,3-diethyl-5-[4-(2-ethylhexyloxycarbonylphenylamino)]-methylene-barbituricacid;

1,3-diethyl-5-(4-n-octadecyloxycarbonylphenylamino)-methylene-barbituricacid;

1,3-dimethyl-5-(4-methoxyethylcarbonylphenylamino)-methylene-barbituricacid;

1,3-dimethyl-5-(4-ethoxyethylcarbonylphenylamino)-methylene-barbituricacid;

1,3-dimethyl-5-(4-methoxycarbomethyloxycarbonylphenylamino)-methylene-barbituricacid;

1,3-dimethyl-5-(4-ethoxycarbomethyloxycarbonylphenylamino)-methylene-barbituricacid;

1,3-diethyl-5-(4-methoxyethylcarbonylphenylamino)-methylene-barbituricacid;

1,3-diethyl-5-(4-ethoxyethylcarbonylphenylamino)-methylene-barbituricacid;

1,3-diethyl-5-(4-methoxycarbomethyloxycarbonylphenylamino)-methylene-barbituricacid;

1,3-diethyl-5-(4-ethoxycarbomethyloxycarbonylphenylamino)-methylene-barbituricacid, and so on.

Of the aminomethylene derivatives represented by the general formula (I)used in the present invention, concrete examples of aminomethylenechroman derivatives in which A in the formula (I) is (d), represented bythe formula (Id): ##STR12## wherein R⁶, n and R are as defined above,include following compounds:

3-(4-ethoxycarbonylphenylaminomethylene)chroman-2,4-dione;

3-(4-isopropoxycarbonylphenylaminomethylene)chroman-2,4-dione;

3-(4-isobutoxycarbonylphenylaminomethylene)chroman-2,4-dione;

3-(4-sec-butoxycarbonylphenylaminomethylene)chroman-2,4-dione;

3-(4-tert-butoxycarbonylphenylaminomethylene)chroman-2,4-dione;

3-(4-n-pentyloxycarbonylphenylaminomethylene)chroman-2,4-dione;

3-(4-n-hexyloxycarbonylphenylaminomethylene)chroman-2,4-dione;

3-(4-n-heptyloxycarbonylphenylaminomethylene)chroman-2,4-dione;

3-(4-n-nonyloxycarbonylphenylaminomethylene)chroman-2,4-dione;

3-(4-n-decyloxycarbonylphenylaminomethylene)chroman-2,4-dione;

3-(4-n-undecyloxycarbonylphenylaminomethylene)chroman-2,4-dione;

3-(4-n-dodecyloxycarbonylphenylaminomethylene)chroman-2,4-dione;

3-(4-n-tridecyloxycarbonylphenylaminomethylene)chroman-2,4-dione;

3-(4-n-tetradecyloxycarbonylphenylaminomethylene)chroman-2,4-dione;

3-(4-n-pentadecyloxycarbonylphenylaminomethylene)chroman-2,4-dione;

3-(4-n-hexadecyloxycarbonylphenylaminomethylene)chroman-2,4-dione;

3-(4-n-heptadecyloxycarbonylphenylaminomethylene)chroman-2,4-dione;

3-(4-methoxycarbonylphenylaminomethylene)chroman-2,4-dione;

3-(4-ethoxycarbonylphenylaminomethylene)chroman-2,4-dione;

3-(4-methoxyethylcarbonylphenylaminomethylene)chroman-2,4-dione;

3-(4-ethoxyethylcarbonylphenylaminomethylene)chroman-2,4-dione;

3-(4-methoxycarbonylmethyloxycarbonylphenylaminomethylene)-chroman-2,4-dione;

3-(4-ethoxycarbonylmethyloxycarbonylphenylaminomethylene)-chroman-2,4-dione;

3-(4-ethoxycarbonylmethyloxycarbonylphenylaminomethylene)-chroman-2,4-dione;and

5- or 6- or 7- or8-methyl-3-(4-ethoxycarbonylphenylamino-methylene)chroman-2,4-dione;

5- or 6- or 7- or8-methyl-3-(4-n-propoxycarbonylphenylaminomethylene)chroman-2,4-dione;

5- or 6- or 7- or8-methyl-3-(4-n-butoxycarbonylphenylaminomethylene)chroman-2,4-dion;

5- or 6- or 7- or8-ethyl-3-(4-methoxycarbonylphenylaminomethylene)chroman-2,4-dione;

5- or 6- or 7- or8-ethyl-3-(4-ethoxycarbonylphenylaminomethylene)chroman-2,4-dione;

5- or 6- or 7- or8-ethyl-3-(4-n-propoxycarbonylphenylaminomethylene)chroman-2,4-dione;

5- or 6- or 7- or8-chloro-3-(4-ethoxycarbonylphenylaminomethylene)chroman-2,4-dione;

5- or 6- or 7- or8-chloro-3-(4-n-propoxycarbonylphenylaminomethylene)chroman-2,4-dione;

5- or 6- or 7- or8-chloro-3-(4-n-butoxycarbonylphenylaminomethylene)chroman-2,4-dione;

5- or 6- or 7- or8-methoxy-3-(4-ethoxycarbonylphenylaminomethylene)chroman-2,4-dione;

5- or 6- or 7- or8-methoxy-3-(4-n-propoxycarbonylphenylaminomethylene)chroman-2,4-dion;

5- or 6- or 7- or8-methoxy-3-(4-n-butoxycarbonylphenylaminomethylene)chroman-2,4-dione;

5- or 6- or 7- or8-acetyl-3-(4-methoxycarbonylphenylaminomethylene)chroman-2,4-dione;

5- or 6- or 7- or8-acethyl-3-(4-ethoxycarbonylphenylaminomethylene)chroman-2,4-dione;

5- or 6- or 7- or8-acetyl-3-(4-n-propoxycarbonylphenylaminomethylene)chroman-2,4-dione;

5- or 6- or 7- or8-methylamino-3-(4-ethoxycarbonylphenylaminomethylene)chroman-2,4-dione;

5- or 6- or 7- or8-methylamino-3-(4-n-propoxycarbonylphenylaminomethylene)chroman-2,4-dione;

5- or 6- or 7- or8-methylamino-3-(4-n-butoxycarbonylphenylaminomethylene)chroman-2,4-dione;

5- or 6- or 7- or8-acethylamino-3-(4-methoxycarbonylphenylaminomethylene)chroman-2,4-dione;

5- or 6- or 7- or8-acethylamino-3-(4-ethoxycarbonylphenylaminomethylene)chroman-2,4-dione;

5- or 6- or 7- or8-acethylamino-3-(4-n-propoxycarbonylphenylaminomethylene)chroman-2,4-dione;

5- or 6- or 7- or8-dimethylamino-3-(4-ethoxycarbonylphenylaminomethylene)chroman-2,4-dione;

5- or 6- or 7- or8-dimethylamino-3-(4-n-propoxycarbonylphenylaminomethylene)chroman-2,4-dione;

5- or 6- or 7- or8-dimethylamino-3-(4-n-butoxycarbonylphenylaminomethylene)chroman-2,4-dione;

5- or 6- or 7- or8-phenylamino-3-(4-methoxycarbonylphenylaminomethylene)chroman-2,4-dione;

5- or 6- or 7- or8-phenylamino-3-(4-ethoxycarbonylphenylaminomethylene)chroman-2,4-dione;

5- or 6- or 7- or8-phenylamino-3-(4-n-propoxycarbonylphenylaminomethylene)chroman-2,4-dione,and so on.

Of the aminomethylene derivatives represented by the general formula (I)used in the present invention, concrete examples of aminomethylenedioxane derivatives in which A in the formula (I) is (e), represented bythe formula (Ie): ##STR13## wherein R⁷, R⁸ and R are as defined above,include following compounds:

2,2-dimethyl-5-(ethoxycarbonylphenylaminomethylene)-1,3-dioxane-4,6-dione;

2,2-dimethyl-5-(4-isopropoxycarbonylphenylaminomethylene)-1,3-dioxane-4,6-dione;

2,2-dimethyl-5-(4-isobutoxycarbonylphenylaminomethylene)-1,3-dioxane-4,6-dione;

2,2-dimethyl-5-(4-sec-butoxycarbonylphenylaminomethylene)-1,3-dioxane-4,6-dione;

2,2-dimethyl-5-(4-tert-butoxycarbonylphenylaminomethylene)-1,3-dioxane-4,6-dione;

2,2-dimethyl-5-(4-n-pentyloxycarbonylphenylaminomethylene)-1,3-dioxane-4,6-dione;

2,2-dimethyl-5-(4-n-hexyloxycarbonylphenylaminomethylene)-1,3-dioxane-4,6-dione;

2,2-dimethyl-5-(4-n-heptyloxycarbonylphenylaminomethylene)-1,3-dioxane-4,6-dione;

2,2-dimethyl-5-(4-n-nonyloxycarbonylphenylaminomethylene)-1,3-dioxane-4,6-dione;

2,2-dimethyl-5-(4-n-decyloxycarbonylphenylaminomethylene)-1,3-dioxane-4,6-dione;

2,2-dimethyl-5-(4-n-undecyloxycarbonylphenylaminomethylene)-1,3-dioxane-4,6-dione;

2,2-dimethyl-5-(4-n-dodecyloxycarbonylphenylaminomethylene)-1,3-dioxane-4,6-dione;

2,2-dimethyl-5-(4-n-tridecyloxycarbonylphenylaminomethylene)-1,3-dioxane-4,6-dione;

2,2-dimethyl-5-(4-n-tetradecyloxycarbonylphenylaminomethylene)-1,3-dioxane-4,6-dione;

2,2-dimethyl-5-(4-n-pentadecyloxycarbonylphenylaminomethylene)-1,3-dioxane-4,6-dione;

2,2-dimethyl-5-(4-n-hexadecyloxycarbonylphenylaminomethylene)-1,3-dioxane-4,6-dione;

2,2-dimethyl-5-(4-n-heptadecyloxycarbonylphenylaminomethylene)-1,3-dioxane-4,6-dione;

2,2-diethyl-5-(4-methoxycarbonylphenylaminomethylene)-1,3-dioxane-4,6-dione;

2,2-diethyl-5-(4-ethoxycarbonylphenylaminomethylene)-1,3-dioxane-4,6-dione;

2,2-diethyl-5-(4-n-propoxycarbonylphenylaminomethylene)-1,3-dioxane-4,6-dione;

2,2-diethyl-5-(4-isopropoxycarbonylphenylaminomethylene)-1,3-dioxane-4,6-dione;

2,2-diethyl-5-(4-n-butoxycarbonylphenylaminomethylene)-1,3-dioxane-4,6-dione;

2,2-diethyl-5-(4-n-pentyloxycarbonylphenylaminomethylene)-1,3-dioxane-4,6-dione;

2,2-diethyl-5-(4-n-hexyloxycarbonylphenylaminomethylene)-1,3-dioxane-4,6-dione;

2,2-diethyl-5-(4-n-heptyloxycarbonylphenylaminomethylene)-1,3-dioxane-4,6-dione;

2,2-diethyl-5-[4-(2-ethylhexyloxycarbonylphenylaminomethylene)]-1,3-dioxane-4,6-dione;

2,2-diethyl-5-(4-n-octadecyloxycarbonylphenylaminomethylene)-1,3-dioxane-4,6-dione;

2,2-dimethyl-5-(4-methoxyethylcarbonylphenylaminomethylene)-1,3-dioxane-4,6-dione;

2,2-dimethyl-5-(4-ethoxyethylcarbonylphenylaminomethylene)-1,3-dioxane-4,6-dione;

2,2-dimethyl-5-(4-methoxycarbomethyloxycarbonylphenylaminomethylene)-1,3-dioxane-4,6-dione;

2,2-dimethyl-5-(4-ethoxycarbomethyloxycarbonylphenylaminomethylene)-1,3-dioxane-4,6-dione;

2,2-diethyl-5-(4-methoxyethylcarbonylphenylaminomethylene)-1,3-dioxane-4,6-dione;

2,2-diethyl-5-(4-ethoxyethylcarbonylphenylaminomethylene)-1,3-dioxane-4,6-dione;

2,2-diethyl-5-(4-methoxycarbomethyloxycarbonylphenylaminomethylene)-1,3-dioxane-4,6-dione;

2,2-diethyl-5-(4-ethoxycarbomethyloxycarbonylphenylaminomethylene)-1,3-dioxane-4,6-dione,and so on.

Of the starting materials employed in the manufacture of the compoundsrepresented by the general formula (I), the compounds of formula (II)are concretely illustrated below.

The starting materials employed in the manufacture of the compounds offormula (Ia) are represented by the formula (IIa'): ##STR14## andinclude following compounds as concrete examples: 1,3-cyclohexanedione,5,5-dimethyl-1,3-cyclohexanedione, 5,5-diethyl-1,3-cyclohexanedione,5,5-di-n-propyl-1,3-cyclohexanedione,5,5-di-isopropyl-1,3-cyclohexanedione,5,5-di-n-butyl-1,3-cyclohexanedione,5,5-di-isobutyl-1,3-cyclohexanedione,5,5-di-sec-butyl-1,3-cyclohexanedione,5,5-di-n-pentyl-1,3-cyclohexanedione,5,5-di-n-hexyl-1,3-cyclohexanedione,5,5-di-n-heptyl-1,3-cyclohexanedione,5,5-di-n-octyl-1,3-cyclohexanedione, 5,5-diphenyl-1,3-cyclohexanedione,5,5-dibenzyl-1,3-cyclohexanedione,5,5-dicyclohexyl-1,3-cyclohexanedione,5,5-di-o-tolyl-1,3-cyclohexanedione,5,5-di-m-tolyl-1,3-cyclo-hexanedione,5,5-di-p-tolyl-1,3-cyclohexanedione,5,5-di-o-anisyl-1,3-cyclohexanedione,5,5-di-m-anisyl-1,3-cyclohexanedione,5,5-di-p-anisyl-1,3-cyclohexanedione,5,5-di-o-chlorophenyl-1,3-cyclohexanedione,5,5-di-m-chlorophenyl-1,3-cyclo-hexanedione,5,5-di-p-chlorophenyl-1,3-cyclohexanedione,5,5-di-o-bromophenyl-1,3-cyclohexanedione,5,5-di-m-bromophenyl-1,3-cyclohexanedione,5,5-di-p-bromophenyl-1,3-cyclohexanedione,5,5-di-(2-methylcyclohexyl)-1,3-cyclohexanedione,5,5-di-(3-methylcyclohexyl)-1,3-cyclohexanedione,5,5-di-(4-methylcyclohexyl)-1,3-cyclohexanedione and so on.

The starting materials employed in the manufacture of the compounds offormula (Ib) are represented by the formula (IIb'): ##STR15## andinclude following compounds as concrete examples:4-hydroxy-6-methyl-2-pyrone, 4-hydroxy-6-ethyl-2-pyrone,4-hydroxy-6-n-propyl-2-pyrone, 4-hydroxy-6-isopropyl-2-pyrone,4-hydroxy-6-n-butyl-2-pyrone, 4-hydroxy-6-isobutyl-2-pyrone,4-hydroxy-6-sec-butyl-2-pyrone, 4-hydroxy-6-n-pentyl-2-pyrone,4-hydroxy-6-n-hexyl-2-pyrone, 4-hydroxy-6-n-heptyl-2-pyrone,4-hydroxy-6-n-octyl-2-pyrone, 4-hydroxy-6-(2-ethylhexyl)-2-pyrone,4-hydroxy-6-cyclopentyl-2-pyrone, 4-hydroxy-6-cyclohexyl-2-pyrone,4-hydroxy-6-allyl-2-pyrone, 4-hydroxy-6-benzyl-2-pyrone,4-hydroxy-6-phenylethyl-2-pyrone, 4-hydroxy-6-phenyl-propyl-2-pyrone,4-hydroxy-6-phenyl-2-pyrone, 4-hydroxy-6-o-tolyl-2-pyrone,4-hydroxy-6-m-tolyl-2-pyrone, 4-hydroxy-6-p-tolyl-2-pyrone,4-hydroxy-6-o-chlorophenyl-2-pyrone,4-hydroxy-6-m-chlorophenyl-2-pyrone,4-hydroxy-6-p-chlorophenyl-2-pyrone, 4-hydroxy-6-o-bromophenyl-2-pyrone,4-hydroxy-6-m-bromophenyl-2-pyrone, 4-hydroxy-6-p-bromophenyl-2-pyrone,4-hydroxy-6-o-anisyl-2-pyrone, 4-hydroxy-6-m-anisyl-2-pyrone,4-hydroxy-6-p-anisyl-2-pyrone, 4-hydroxy-6-o-phenethyl-2-pyrone,4-hydroxy-6-m-phenethyl-2-pyrone, 4-hydroxy-6-p-phenethyl-2-pyrone andso on.

The starting materials employed in the manufacture of the compounds offormula (Ic) are represented by the formula (IIc'): ##STR16## andinclude following compounds as concrete examples: barbituric acid,1,3-dimethylbarbituric acid, 1,3-diethylbarbituric acid,1,3-di-n-propylbarbituric acid, 1,3-di-iso-propylbarbituric acid,1,3-di-n-butylbarbituric acid, 1,3-di-isobutylbarbituric acid,1,3-di-sec-butylbarbituric acid, 1,3-di-n-pentylbarbituric acid,1,3-di-n-hexylbarbituric acid, 1,3-di-n-heptylbarbituric acid,1,3-di-n-octylbarbituric acid, 1,3-diphenylbarbituric acid,1,3-dibenzylbarbituric acid, 1,3-dicyclohexylbarbituric acid,1,3-di-o-tolylbarbituric acid, 1,3-di-m-tolylbarbituric acid,1,3-di-p-tolylbarbituric acid, 1,3-di-o-anisylbarbituric acid,1,3-di-m-anisylbarbituric acid, 1,3-di-p-anisylbarbituric acid,1,3-di-o-chlorophenylbarbituric acid, 1,3-di-m-chlorophenylbarbituricacid, 1,3-di-p-chlorophenylbarbituric acid,1,3-di-o-bromophenylbarbituric acid, 1,3-di-m-bromophenylbarbituricacid, 1,3-di-allylbarbituric acid, 1,3-di-(2-methylcyclohexyl)barbituricacid, 1,3-di-(3-methylcyclohexyl)barbituric acid,1,3-di-(4-methylcyclohexyl)barbituric acid and so on.

The starting materials employed in the manufacture of the compounds offormula (Id) are represented by the formula (IId'): ##STR17## andinclude following compounds as concrete examples: 4-hydroxycoumarin,4,5-dihydroxycoumarin, 4,6-dihydroxycoumarin, 4,7-dihydroxycoumarin,4-hydroxy-5-methoxycoumarin, 4-hydroxy-6-methoxycoumarin,4-hydroxy-7-methoxycoumarin, 4-hydroxy-5-methylcoumarin,4-hydroxy-6-methylcoumarin, 4-hydroxy-7-methylcoumarin,4-hydroxy-5-methoxycarbonylcoumarin,4-hydroxy-6-methoxycarbonylcoumarin,4-hydroxy-7-methoxycarbonylcoumarin, 4-hydroxy-5-ethoxycarbonylcoumarin,4-hydroxy-6-ethoxycarbonylcoumarin, 4-hydroxy-7-ethoxycarbonylcoumarin,4-hydroxy-5-acetylcoumarin, 4-hydroxy-6-acetylcoumarin,4-hydroxy-7-acetylcoumarin, 4-hydroxy-5-aminocoumarin,4-hydroxy-6-aminocoumarin, 4-hydroxy-7-aminocoumarin,4-hydroxy-5-dimethylaminocoumarin, 4-hydroxy-6-dimethylaminocoumarin,4-hydroxy-7-dimethylaminocoumarin, 4-hydroxy-5-diethylaminocoumarin,4-hydroxy-6-diethylaminocoumarin, 4-hydroxy-7-diethylaminocoumarin,4-hydroxy-5-di-n-propylaminocoumarin,4-hydroxy-6-di-n-propylaminocoumarin,4-hydroxy-7-di-n-propylaminocoumarin,4-hydroxy-5-di-n-butylaminocoumarin,4-hydroxy-6-di-n-butylaminocoumarin,4-hydroxy-7-di-n-butylaminocoumarin, 4-hydroxy-5-methylaminocoumarin,4-hydroxy-6-methylaminocoumarin, 4-hydroxy-7-methylaminocoumarin,4-hydroxy-5-ethylaminocoumarin, 4-hydroxy-6-ethylaminocoumarin,4-hydroxy-7-ethylaminocoumarin, 4-hydroxy-5-phenylaminocoumarin,4-hydroxy-6-phenylaminocoumarin, 4-hydroxy-7-phenylaminocoumarin,4-hydroxy-5-chlorocoumarin, 4-hydroxy-6-chlorocoumarin,4-hydroxy-7-chlorocoumarin, 4-hydroxy-5-bromocoumarin,4-hydroxy-6-bromocoumarin, 4-hydroxy-7-bromocoumarin and so on.

The starting materials employed in the manufacture of the compounds offormula (Ie) are represented by the formula (IIe'): ##STR18## andinclude following compounds as concrete examples:2,2-dimethy-1,3-dioxane-4,6-dione, 2,2-diethy-1,3-dioxane-4,6-dione,2,2-di-n-propyl-1,3-dioxane-4,6-dione,2,2-di-isopropyl-1,3-dioxane-4,6-dione,2,2-di-n-butyl-1,3-dioxane-4,6-dione,2,2-di-isobutyl-1,3-dioxane-4,6-dione,2,2-di-sec-butyl-1,3-dioxane-4,6-dione,2,2-di-n-pentyl-1,3-dioxane-4,6-dione,2,2-di-n-hexyl-1,3-dioxane-4,6-dione,2,2-di-n-heptyl-1,3-dioxane-4,6-dione,2,2-di-n-octyl-1,3-dioxane-4,6-dione,2,2-di-(2-ethylhexyl)-1,3-dioxane-4,6-dione,2,2-dicyclopentyl-1,3-dioxane-4,6-dione,2,2-dicyclohexyl-1,3-dioxane-4,6-dione,2,2-diphenyl-1,3-dioxane-4,6-dione, 2,2-dibenzyl-1,3-dioxane-4,6-dione,2,2-diphenylethyl-1,3-dioxane-4,6-dione,2,2-diphenylpropyl-1,3-dioxane-4,6-dione,2,2-di-o-anisyl-1,3-dioxane-4,6-dione,2,2-di-m-anisyl-1,3-dioxane-4,6-dione,2,2-di-p-anisyl-1,3-dioxane-4,6-dione,2,2-di-o-phenethyl-1,3-dioxane-4,6-dione,2,2-di-m-phenethyl-1,3-dioxane-4,6-dione,2,2-di-p-phenethyl-1,3-dioxane-4,6-dione,2,2-di-o-chlorophenyl-1,3-dioxane-4,6-dione,2,2-di-m-chlorophenyl-1,3-dioxane-4,6-dione,2,2-di-p-chlorophenyl-1,3-dioxane-4,6-dione,2,2-di-o-bromophenyl-1,3-dioxane-4,6-dione,2,2-di-m-bromophenyl-1,3-dioxane-4,6-dione,2,2-di-p-bromophenyl-1,3-dioxane-4,6-dione,2,2-di-o-tolyl-1,3-dioxane-4,6-dione,2,2-di-m-tolyl-1,3-dioxane-4,6-dione,2,2-di-p-tolyl-1,3-dioxane-4,6-dione and so on.

The compounds of formula (III) described above which are anotherstarting materials employed in the manufacture of the compounds offormula (I), include following compounds as concrete examples: methylN-formylaminobenzoate, ethyl N-formylaminobenzoate, n-propylN-formylaminobenzoate, isopropyl N-formylaminobenzoate, n-butylN-formylaminobenzoate, isobutyl N-formylaminobenzoate, sec-butylN-formylaminobenzoate, tert-butyl N-formylaminobenzoate, n-pentylN-formylaminobenzoate, n-hexyl N-formylaminobenzoate, n-heptylN-formylaminobenzoate, n-octyl N-formylaminobenzoate, 2-ethylhexylN-formylaminobenzoate, n-nonyl N-formylaminobenzoate, n-nonylN-formylaminobenzoate, n-decyl N-formylaminobenzoate, n-undecylN-formylaminobenzoate, n-dodecyl N-formylaminobenzoate, n-tetradecylN-formylaminobenzoate, n-pentadecyl N-formylaminobenzoate, n-hexadecylN-formylaminobenzoate, n-heptadecyl N-formylaminobenzoate, n-octadecylN-formylaminobenzoate, n-nanodecyl N-formylaminobenzoate, benzylN-formylaminobenzoate, phenethyl N-formylaminobenzoate, phenyl-propylN-formylaminobenzoate, phenyl N-formylaminobenzoate, o-anisylN-formylaminobenzoate, m-anisyl N-formylaminobenzoate, p-anisylN-formylaminobenzoate, o-tolyl N-formylaminobenzoate, m-tolylN-formylaminobenzoate, p-tolyl N-formylaminobenzoate, o-phenethylN-formylaminobenzoate, m-phenethyl N-formylaminobenzoate, p-phenethylN-formylaminobenzoate, cyclopentyl N-formylaminobenzoate, cyclohexylN-formylaminobenzoate, methoxyethyl N-formylaminobenzoate, ethoxyethylN-formylaminobenzoate, methoxycarbonylmethyl N-formylaminobenzoate,ethoxycarbonylmethyl N-formylaminobenzoate and so on.

Examples of antioxidants which can be added in addition to compoundsaccording to the present invention include following compounds:

2,6-di-tert-butyl-4-methylphenol;

2-tert-butyl-4,6-dimethylphenol;

2,6-di-tert-butyl-4-ethylphenol;

2,6-di-tert-butyl-4-n-butylphenol;

2,6-di-tert-butyl-4-isobutylphenol;

2,6-di-cyclopentyl-4-methylphenol;

2-(α-methylcyclohexyl)-4,6-dimethylphenol;

2,6-dioctadecyl-4-methylphenol;

2,4,6-tricyclohexylphenol;

2,6-dinonyl-4-methyphenol;

2,6-di-tert-butyl-4-methoxymethylphenol;

2,4-dimethyl-6-(1'-methyl-undeca-1'-yl)-phenol;

2,4-dimethyl-6-(1'-methyl-heptadeca-1'-yl)-phenol;

2,4-dimethyl-6-(1'-methyl-trideca-1'-yl)-phenol and mixture thereof;

2,4-di-octylthiomethyl-6-tert-butylphenol;

2,4-di-octylthiomethy-6-methylphenol;

2,4-di-octylthiomethy-6-ethylphenol;

2,6-di-dodecylthiomethyl-4-nonylphenol and mixutre thereof;

2,6-di-tert-butyl-4-methoxyphenol;

2,5-di-tert-butylhydroquinone;

2,5-di-tert-amylhydroquinone;

2,6-diphenyl-4-octadecyloxyphenol;

2,6-di-tert-butylhydroquinone;

2,5-di-tert-butyl-4-hydroxyanisole;

3,5-di-tert-butyl-4-hydroxyanisole;

3,5-di-tert-butyl-4-hydroxyphenylstearate;

bis(3,5-di-tert-butyl-4-hydroxyphenyl)adipate and mixture thereof;

2,4-bis-octylmercapt-6-(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-trizine;

2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-trizine;

2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,3,5-triazine;

2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,2,3-triazine;

1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-isocyanurate;

1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-isocyanurate;

2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenylethyl)-1,3,5-triazine;

1,3,5-tris(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hexahydro-1,3,5-triazine;

1,3,5-tris(3,5-dicyclohexyl-4-hydroxybenzyl)-isocyanurate or the like;and

2,2'-methylenebis(6-tert-butyl-4-methylphenol);

2,2'-methylenebis(6-tert-butyl-4-ethylphenol);

2,2'-ethylidenebis(4,6-di-tert-butylphenol);

2,2'-ethylidenebis(6-tert-butyl-4-isobutylphenol);

4,4'-methylenebis(2,6-di-tert-butylphenol);

4,4'-methylenebis(6-tert-butyl-2-methylphenol);1,1-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)butane;

ethylene glycol bis[3,3'-bis(3'-tert-butyl-4'-hydroxyphenyl)butylate]orthe like; and

1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene;

1,4-bis(3,5-di-tert-butyl-4-hydroxybenzyl)-2,3,5,6-tetramethylbenzene;

2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)phenol or the like.

Examples of light stabilizing agents which can be added in addition tocompounds according to the present invention include followingcompounds:

2-(2'-hydroxy-5'-methylphenyl)benzotriazole,2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)benzotriazole,2-(5'-tert-butyl-2'-hydroxyphenyl)benzotriazole,2-[2'-hydroxy-5'-(1,1,3,3-tetra-methylbutyl)phenyl]benzotriazole,2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)-5-chlorobenzotriazole,2-(3'-tert-butyl-2'-hydroxy-5'-methyphenyl)-5-chlorobenzotriazole,2-(2'-hydroxy-4'-octoxyphenyl)benzotriazole,2-(3',5'-di-tert-amyl-2'-hydroxyphenyl)benzotriazole,2-[3'-tert-butyl-2'-hydroxy-5'-(2'-octyloxycarbonylethylphenyl)-5-chlorobenzotriazoleor the like;

4-hydroxy-, 4-methoxy-, 4-octoxy-, 4-decyloxy-, 4-dodecyloxy-,4-benzyloxy-, 4,2',4'-trihydroxy-, 2'-hydroxy-4,4'-dimethoxy- or4-(2-ethylhexyloxy)-2-hydroxybenzophenone derivatives or the like;

4-tert-butylphenyl salicylate, phenyl salicylate, octylphenylsalicylate, dibenzoyl resorcinol, bis(4-tert-butylbenzoyl resorcinol,2,4-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate, hexadecyl3,5-di-tert-butyl-4-hydroxybenzoate or the like; ethyl α-cyano-β,β-diphenylacrylate, isooctyl α-cyano-β, β-diphenylacrylate, methylα-carbomethoxycinnamate, methyl α-cyano-β-methyl-p-methoxycinnamate orthe like; bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate,bis(2,2,6,6-tetramethyl-4-piperidyl)succinate,bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate,bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl)sebacate,bis(1,2,2,6,6-pentamethyl-4-piperidyl)adipate or the like;

4,4'-di-octyloxyoxanilide, 2,2'-diethoxyoxyoxanilide,2,2'-di-octyloxy-5,5'-di-tert-butyloxanilide,2,2'-di-dodecyloxy-5,5'-di-tert-butyloxanilide,2-ethoxy-2'-ethyloxanilide, N,N'-bis-(3-dimethylaminopropyl)oxanilide,2-ethoxy-5-tert-butyl-2'-ethoxyoxanilide or the like;

2,4,6-tris(2-hydroxy-4-octyloxyphenyl)-1,3,5-triazine,2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethyl-phenyl)-1,3,5-triazine,2,4-bis(2-hydroxy-4-propyloxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazine,2-(2-hydroxy-4-dodecyloxy-phenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazineor the like.

Example of metal inactivators which can be added in addition tocompounds according to the present invention include,N,N'-diphenyloxamide, N-salcylal-N'-salicyloyl-hydrazine,N,N'-bis(salicyloyl)hydrazine,N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazine,3-salicylolyamino-1,2,3-triazole, bis(benzylidene)oxalic acid hydrazide,isophthalic acid dihydrazide, N,N'-diacetal-adipic acid dihydrazide,N,N'-bis-salicyloyloxalic acid dihydrazide,N,N'-bis(salicyloyl)thiopropionic acid dihidrazide or the like.

Examples of peroxide scavengers which can be added in addition tocompounds according to the present invention include, dilaurylthiodipropionate, distearyl thiodipropionate, dimyristylthiodipropionate or ditridecyl thiodipropionate,2-mercaptobenzimidazole,pentaerythritoltetrakis(dodecyl-mercapto)propionate or the like.

The aminomethylene derivatives of the present invention have preferredchracteriscits, that they have much higher ultraviolet absorptioncompared to that of conventionally known ultraviolet absorbent for UV-Arange, as the maximum absorption range of aminomethylene cyclohexanederivatives of the present invention represented by the general formula(I) in which A is (a) is 340 to 360 nm, the maximum absorption range ofaminomethylene pyrone derivatives of the present invention representedby the general formula (I) in which A is (b) is 340 to 360 nm, and themaximum absorption range of aminomethylene barbituric acid derivativesof the present invention represented by the general formula (I) in whichA is (c) is 340 to 360 nm, the maximum absorption range ofaminomethylene chroman derivatives of the present invention representedby the general formula (I) in which A is (d) is 340 to 380 nm, and themaximum absorption range of aminomethylene dioxane derivatives of thepresent invention represented by the general formula (I) in which A is(e) is 330 to 350 nm, and the present compounds have lower irritabilityand no other toxicity, higher compatibility to other cosmetic bases, andsmaller percutaneous absorption.

The base for skin ointment which is also the cosmetic materialsaccording to the present invention can be any that is inactive to abovedescribed aminomethylene derivatives (I), and can be solid, liquid,emulsion, foaming solution, gel or the like. Examples of the cosmeticbase of the present invention include olive oil, tsubaki oil, cottonseed oil, castor oil, soybean oil, coconut oil, cacao butter, lanoline,bees wax, carnauba wax, hardened oil, stearic acid, palmitic acid,myristic acid, ascorbic acid, behenic acid, and esters or metal saltsthereof, higher alcohol including decylethyl, oleyl, lauryl, cetyl orstearyl alcohol. Examples of other base include synthetic oil such assqualene monostearic acid glyceride, synthetic polyether oils, sorbitanmonooleate, lanoline and hydrogenated forms thereof and squalenes;mineral oil such as paraffin, petrolatum, liquid paraffin, microcrystalwax or the like. Further, other examples of base which can be usedinclude silicone oil, polyethers, dialkylsiloxanes, fine powders ofstarch or talc, carbohydrate with lower boiling point or carbohydratecontaining halogen both of which are used as a switchsbout type powerpropellant.

Examples of the humectants include glycerin, propylene glycol, sorbitol,polyethylene glycol, sodium pyrrolidone carboxylate or the like.Examples of sticking agents include polyvinyl alcohol, sodium salt ofcarboxymethyl cellulose, sodium alginate, propylene glycol ester or thelike.

Examples of the preservatives include benzoic acid, sorbic acid,dehydroacetic acid, p-hydroxy benzoic acid esters or the like. Examplesof the solvent include ethanol, acetone, acetates, isopropanol or thelike.

Examples of ultraviolet absorbent which can be combinedly used includebenzotriazoles such as 2-(2'-hydroxy-5'-methylphenyl)benzotriazole,2-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole,2-(2'-hydroxy-3',5'-di-tert-butylphenyl)-5-chlorobenzotriazole,2-(2'-hydroxy-3',5'-di-tert-butylphenyl)benzotriazole,2-(2'-hydroxy-4'-n-octoxyphenyl)-benzotriazole or the like;

benzophenones such as 2-hydroxy-4-methoxy-2'-carboxybenzophenone,2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone,2,2'-dihydroxy-4,4'-dimethoxybenzophenone,2,2'-dihydroxy-4,4'-dimethoxy-5-sulfobenzophenone,2-hydroxy-4-methoxybenzophenone-5-sulfonic acid,2-hydroxy-4-octadecyloxybenzophenone,2,2',4,4'-tetrahydroxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone,2-hydroxy-4-(2-hydroxy-3-methacryloxy)propoxybenzophenone or the like;

compounds belonging to benzoic acid family such as methyl o-benzoylbenzoate, p-aminobenzoic acid, glyceryl p-aminobenzoate, ethylp-aminobenzoate, 2-ethylhexyl p-dimethylaminobenzoate, octylp-dimethylaminobenzoate, ethyl 4-bis(hydroxybutyl)aminobenzoate, methylo-aminobenzoate or the like; compounds belonging to cinnamic acid familysuch as benzyl cinnamate, p-methoxycinnamic acid diethanolamine,2-ethylhexyl p-methoxycinnamate, isopropyl p-methoxycinnamate or thelike; and

other acid esters such as gallic acid triesters, 2-ethylhexylsalicylate, 3,3,5-trimethylcyclohexyl salicylate, salicylic acidtriethanolamine, p-butylphenyl salicylate, 2-ethylhexyl2-cyano-3,3-diphenylacrylate, 2-ethylhexyl 3-cyano-3,3-diphenylacrylateor the like.

Cosmetic materials containing above described aminomethylene derivatives(I) of the present invention are produced by adding the same to abovedescribed known cosmetic base using an ordinary method to prepare cream,solution, oil, spray, stick, emulsion, foundation, and ointment.

Formulation ratio of above described aminomethylene derivatives (I) inthe cosmetic materials of the present invention can differ according tothe form of use and is not limited, and can be any amount that iseffective, and in general the aminomethylene derivatives is added to thecomposition at a ratio of 0.1 to 20 weight %, preferably 0.5 to 5 weight%. Further above described aminomethylene derivatives (I) of the presentinvention can be added alone but more preferable effect can be obtainedby combining with other UV-B absorbents, UV-A absorbents or the like,when it is used for ordinary sunscreen cosmetics. Above describedaminomethylene derivatives (I) of the present invention can be used bycombining with many other additives. Examples of suitable additivesinclude emulsion of W/O type and O/W type. Regarding emulsifiers,commercially available emulsifiers including polyglycerin fatty acidesters, polyoxyethylene lanolin derivatives, polyoxyethylene sorbitanfatty acid esters, polyoxyethylene polyoxypropylene alkylethers,polyoxyethylene-sorbitol fatty acid esters, sucrose fatty acid esters,propylene glycol fatty acid esters or the like. Further, thickenersincluding ethylcellulose, polyacrylic acid, gelatin, agar or the likecan be added if necessary. In addition, perfumes, humectants,emulsifying agents, medically active ingredients and others may beoptionally added.

EXAMPLES

The present invention will be further described with reference to thefollowing examples of synthesis of the compounds of the invention, andcosmetic materials and polymer composition comprising said compounds,however these examples are intended to show some preferred embodimentsand are not to be constructed to limit the scope of the invention.

Example 1

Synthesis of2-(4-methoxycarbonylphenylamino)-methylene-1,3-cyclohexadione [compoundrepresented by the general formula (I) of which A is (a), R¹ =R²=hydrogen atom and R=methyl]

After stirring suspension containing 0.20 mol of 1,3-cyclohexanedione,0.50 mol of 4-methoxycarbonyl-N-formanilide and 25 ml of toluene, 0.50mol of phosphorus oxychloride is added to the suspension over 15minutes. During the addition, temperature is maintained at 45° C. orlower. The suspension is further stirred for 10 minutes, then 250 ml ofhot solution of toluene containing 0.48 mol of 1,3-cyclohexanedione isadded to at 60 to 65° C., over 45 minutes. The reaction mixture isconstantly stirred and allowed to cool to room temperature, and reactionis terminated by adding the reaction mixture dropwise into 600 ml of 15%sodium hydroxide solution. Obtained organic layer is being washed with200 ml of saturated aqueous solution of sodium chloride. The organiclayer is fractionated, allowed to dry on anhydrous sodium sulfate,filtrated and concentrated to obtaine crude product.

Purified product having the melting point of 198 to 199° C. is obtainedthrough recrystalization from ethanol.

Mass spectrum: m/z 274(M++1, 17%), 273(M+, 96), 242(16), 217(58),202(24), 144(25), 123(19), 89(10);

Ultraviolet absorption spectrum (ethanol): λ max(nm) 358 (ε max 38,000).

Example 2

Synthesis of2-(4-n-propoxycarbonylphenylamino)-methylene-1,3-cyclohexadione[compound represented by the general formula (I) of which A is (a), R¹=R² =hydrogen atom and R=n-propyl]

Title compound was synthesized from 1,3-cyclohexanedione and4-n-propyloxycarbonyl-N-formanilide using the same reaction conditionsand after-treatment used in EXAMPLE 1.

Purified product having the melting point of 147.5 to 148.5° C. wasobtained through recrystalization from ethanol.

Mass spectrum: m/z 302(M++1, 25%), 301(M+, 100), 259(18), 245(52),242(37), 230(18), 203(12), 188(10), 144(26), 123(22), 89(10);

Ultraviolet absorption spectrum (ethanol): λ max(nm) 358 (ε max 34,000).

Example 3

Synthesis of2-(4-n-butoxycarbonylphenylamino)-methylene-1,3-cyclohexadione [compoundrepresented by the general formula (I) of which A is (a), R¹ =R²=hydrogen atom and R=n-butyl]

Title compound was synthesized from 1,3-cyclohexanedione and4-n-butyloxycarbonyl-N-formanilide using the same reaction conditionsand after-treatment used in EXAMPLE 1.

Purified product having the melting point of 144.5 to 146° C. wasobtained through recrystalization from ethanol.

Mass spectrum: m/z 316(M++1, 20%), 315(M+, 100), 260(12), 259(70),242(32), 203(13), 144(15), 123(13);

Ultraviolet absorption spectrum (ethanol): λ max(nm) 358 (ε max 33,800).

Example 4

Synthesis of2-(4-n-octadecyloxycarbonylphenylamino)-methylene-1,3-cyclohexadione[compound represented by the general formula (I) of which A is (a), R¹=R² =hydrogen atom and R=n-octadecyl]

Title compound was synthesized from 1,3-cyclohexanedione and4-n-octadecyloxycarbonyl-N-formanilide using the same reactionconditions and after-treatment used in EXAMPLE 1.

Purified product having the melting point of 114.5 to 115.5° C. wasobtained through recrystalization from ethanol.

Mass spectrum: m/z 512(M++1, 17%), 511(M+, 48), 389(22), 260(14),242(11), 215(12), 138(26), 137(100), 120(31);

Ultraviolet absorption spectrum (ethanol): λ max(nm) 363 (ε max 27,000).

Example 5

Synthesis of5,5-dimethyl-2-(4-methoxycarbonylphenylamino)-methylene-1,3-cyclohexadione[compound represented by the general formula (I) of which A is (a), R¹=R² =methyl and R=methyl]

Title compound was synthesized from dimedone and4-methoxycarbonyl-N-formanilide using the same reaction conditions andafter-treatment used in EXAMPLE 1.

Purified product having the melting point of 193 to 194.5° C. wasobtained through recrystalization from ethanol.

Mass spectrum: m/z 302(M++1, 20%), 301(M+, 100), 270(12), 217(65),202(16), 151(10), 144(19);

Ultraviolet absorption spectrum (ethanol): λ max(nm) 358 (ε max 50,000).

Example 6

Synthesis of5,5-dimethyl-2-(4-n-propoxycarbonylphenylamino)-methylene-1,3-cyclohexadione[compound represented by the general formula (I) of which A is (a), R¹=R² =methyl and R=n-propyl]

Title compound was synthesized from dimedone and4-n-propyloxycarbonyl-N-formanilide using the same reaction conditionsand after-treatment used in EXAMPLE 1.

Purified product having the melting point of 182 to 183° C. was obtainedthrough recrystalization from ethanol.

Mass spectrum: m/z 330(M++1, 21%), 329(M+, 100), 270(21), 245(43),144(13);

Ultraviolet absorption spectrum (ethanol): λ max(nm) 358 (ε max 49,000).

Example 7

Synthesis of5,5-dimethyl-2-(4-n-butoxycarbonylphenylamino)-methylene-1,3-cyclohexadione[compound represented by the general formula (I) of which A is (a), R¹=R² =methyl and R=n-butyl]

Title compound was synthesized from dimedone and4-n-butyloxycarbonyl-N-formanilide using the same reaction conditionsand after-treatment used in EXAMPLE 1.

Purified product having the melting point of 169.5 to 170° C. wasobtained through recrystalization from ethanol.

Mass spectrum: m/z 344(M++1, 23%), 343(M+, 100), 287(32), 270(23),259(34), 203(12), 144(13);

Ultraviolet absorption spectrum (ethanol): λ max(nm) 358 (εmax 48,700).

Example 8

Synthesis of5,5-dimethyl-2-[4-(2-ethylhexyloxycarbonylphenylamino)]-methylene-1,3-cyclohexadione[compound represented by the general formula (I) of which A is (a), R¹=R² =methyl and R=2-ethylhexyl]

Title compound was synthesized from dimedone and4-(2-ethylhexyloxycarbonyl)-N-formanilide using the same reactionconditions and after-treatment used in EXAMPLE 1.

Purified product having the melting point of 123.5 to 124.5° C. wasobtained through recrystalization from ethanol.

Mass spectrum: m/z 400(M++1, 8%), 399(M+, 39), 288(22), 287(100),270(26), 203(27);

Ultraviolet absorption spectrum (chloroform): λ max(nm) 364 (ε max53,600).

Example 9

Synthesis of5,5-dimethyl-2-(4-n-octadecyloxycarbonylphenylamino)-methylene-1,3-cyclohexadione[compound represented by the general formula (I) of which A is (a), R¹=R² =methyl and R=n-octadecyl]

Title compound was synthesized from dimedone and4-n-octadecyloxycarbonyl-N-formanilide using the same reactionconditions and after-treatment used in EXAMPLE 1.

Purified product having the melting point of 115 to 116.5° C. wasobtained through recrystalization from ethanol.

Mass spectrum: m/z 540(M++1, 39%), 539(M+, 100), 525(12), 524(32),288(28), 271(15), 270(25), 243(36), 137(17), 120(19);

Ultraviolet absorption spectrum (chloroform): λ max(nm) 363 (ε max40,000).

Example 10

Practical examples of formulation of skin ointment according to thepresent invention hereunder will be described.

According to the formulation listed in Table 1, a cosmetic liquidcontaining the compound according to EXAMPLE 8, that is5,5-dimethyl-2-[4-(2-ethylhexyloxycarbonylphenylamino)]-methylene-1,3-cyclohexadioneand as control cosmetic liquids, cosmetic liquids containing compound ofControl 1, that is 2,2',4,4'-tetrahydroxybenzophenone, and compound ofControl 2, that is 2-ethylhexyl p-methoxycinnamate, respectively, wereprepared.

                  TABLE 1                                                         ______________________________________                                        Composition   EXAMPLE 10 Control 1 Control 2                                  ______________________________________                                        ethanol       8.0        8.0       8.0                                          glycerin 2.0 2.0 2.0                                                          citric acid 0.02 0.02 0.02                                                    sodium citrate 0.1 0.1 0.1                                                    methylparaben 0.05 0.05 0.05                                                  POE hardened caster oil 0.5 0.5 0.5                                           perfume some some some                                                        compound of EXAMPLE 8 1.0 -- --                                               compound of Control 1 --  1.0 --                                              compound of Control 2 -- --  1.0                                              propylene glycol 7.0 7.0 7.0                                                  purified water rest rest rest                                               ______________________________________                                    

Control 1 exhibited pale yellow and was not suitable for cosmeticliquid.

Confirmation of Sunscreening Effect

Cosmetic liquid according to EXAMPLE 10 in which compound producedaccording to EXAMPLE 8 and that of Control 2 were, respectively, appliedon the skin and their effect at practical use in beach was tested. Oneach of right or left half area of the back of ten respective male andfemale, each sample solution was applied, and the degree of suntan wasexamined and obtained results was listed in Table 2. According to thedegree of suntan, results were estimated based on the followingestimation criteria.

    ______________________________________                                               Estimation Criteria                                                    ______________________________________                                               no rash    ∘                                                 slight rash Δ                                                           severe rash ×                                                         ______________________________________                                    

                  TABLE 2                                                         ______________________________________                                        Estimation   Area applied with                                                                         Area applied                                           criteria EXAMPLE 10 with Control 2                                          ______________________________________                                        ∘                                                                              17          12                                                     Δ 3 6                                                                   Δ - × 0 2                                                         × 0 0                                                                   Frequency of No itching 7 cases                                               skin trouble  slight rash 1 case                                            ______________________________________                                    

Example 11

Light Stability Effect for Polymer Materials

Each of 0.05, 0.2 and 0.5 part by weight of sample produced according toEXAMPLE 8 was formulated with 100 parts by weight of polyethylene powderor polypropylene powder, mixed well using a mixer, then melted andkneaded using a extruder having the diameter of 25 mm at cylindertemperature of 200° C., and pelletized. Obtained pellets were compactedinto sheets of 0.25 mm thickness at 210° C. to prepare test strips.Obtained test strips were punched into dumbbell shapes accommodating toa tension test. Test strip of control which did not contain lightstabilizing agent was prepared, using the above described same method,and test strips were examined.

Using the WEL-75XS-HS-BEC model xenon sunshine long-life weatherometermanufactured by Suga Shiken-Kiki Co. Ltd., these test strips werelight-irradiated with black panel temperature of 80° C., and wereexamined for lowering in tensile strength over time.

The tension test was performed at 23±2° C., relative humidity of 50±5%,test speed of 50±5.0 mm/minutes, using the DSS-5000 model tension metermanufactured Shimadzu Seisakusho Co. Ltd. Tension strength wascalculated according to the following method.

Equation 1

    Ts=S/T·W

wherein,

Ts=tension strength (kgf/mm²)

T=thickness of samples (mm)

W=wide of samples (mm)

S=maximum strength of samples (kgf)

Obtained results were as listed by Table 3. As apparent from the resultsshown in Table 3, the aminomethylene cyclohexane derivatives accordingto the present invention show prominent stabilizing effect (that is,elongated time to deterioration).

                  TABLE 3                                                         ______________________________________                                                 (unit: kgf)                                                          Name of resin                                                                            200    400     600   800   1000  1200                                 hrs hrs hrs hrs hrs hrs                                                    ______________________________________                                        Polypropylene: no,                                                                       3.15   2.13    0     --    --    --                                  0.05 (wt%) 3.60 3.10 2.90 -- -- --                                            0.2 (wt%) 3.70 3.45 3.40 -- -- --                                             0.5 (wt%) 3.98 3.80 3.65 -- -- --                                             Polyethylene: no, 2.42 2.29 2.25 2.10 1.90 0                                  0.05 (wt%) 2.65 2.56 2.50 2.45 2.30 2.21                                      0.2 (wt%) 2.81 2.70 2.62 2.55 2.42 2.39                                       0.5 (wt%) 2.88 2.80 2.75 2.70 2.63 2.60                                     ______________________________________                                    

Example 12

Synthesis of6-methyl-3-(4-methoxycarbonylphenyaminomethylene)-2H,3H,4H-pyran-2,4-dione[compound represented by general (I) in which A is (b) and R³ =methyl,R=methyl]

Suspension containing 0.20 mol of 4-hydroxy-6-methyl-2-pyrone, 0.50 molof 4-methoxycarbonyl-N-formanilide and 25 ml of toluene was mixed andadded with 0.50 mol of phosphorous oxychloride over 15 minutes. Duringthe addition temperature was maintained at 45° C. or lower. Thesuspension is further stirred for 10 minutes, then 250 ml of hotsolution of toluene containing 0.48 mol of 4-hydroxy-6-methyl-2-pyroneis added to at 60 to 65° C., over 45 minutes. The reaction mixture isconstantly stirred and allowed to cool to room temperature, and reactionis terminated by adding the reaction mixture dropwise into 600 ml of 15%sodium hydroxide solution. Obtained organic layer is being washed with200 ml of saturated aqueous solution of sodium chloride. The organiclayer is fractionated, allowed to dry on anhydrous sodium sulfate,filtrated and concentrated to obtain crude product.

Purified product having the melting point of 251 to 253° C. is obtainedthrough recrystalization from dioxane.

Mass spectrum: m/z 288(M++1, 18%), 287(M+, 100), 256(15), 244(15),202(24), 175(19), 144(41), 137(18), 116(14), 98(34), 89(14), 85(12);

Ultraviolet absorption spectrum (ethanol): λ max(nm) 368 (ε max 51,000).

Example 13

Synthesis of6-methyl-3-(4-n-propoxycarbonylphenylaminomethylene)-2H,3H,4H-pyran-2,4-dione[compound represented by the general formula (I) of which A is (b), R³=methyl and R=n-propyl]

Title compound was synthesized from 4-hydroxy-6-methyl-2-pyrone and4-n-propyloxycarbonyl-N-formanilide using the same reaction conditionsand after-treatment used in EXAMPLE 12.

Purified product having the melting point of 199 to 200° C. was obtainedthrough recrystalization from dioxane.

Mass spectrum: m/z 316(M++1, 22%), 315(M+, 100), 273(28), 272(13),256(33), 230(14), 172(11), 144(27), 137(15), 98(26), 89(10), 85(10);

Ultraviolet absorption spectrum (ethanol): λ max(nm) 368 (ε max 48,300).

Example 14

Synthesis of6-methyl-3-(4-n-butoxycarbonylphenylaminomethylene)-2H,3H,4H-pyran-2,4-dione[compound represented by the general formula (I) of which A is (b), R³=methyl and R=n-butyl]

Title compound was synthesized from 4-hydroxy-6-methyl-2-pyrone and4-n-butyloxycarbonyl-N-formanilide using the same reaction conditionsand after-treatment used in EXAMPLE 12.

Purified product having the melting point of 176.5 to 177° C. wasobtained through recrystalization from dioxane.

Mass spectrum: m/z 330(M++1, 21%), 329(M+, 100), 274(12), 273(73),256(33), 188(11), 172(11), 161(12), 144(26), 137(15), 98(26), 89(10),85(10);

Ultraviolet absorption spectrum (ethanol): λ max(nm) 368 (ε max 77,900).

Example 15

Synthesis of6-methyl-3-(4-n-octadecyloxycarbonylphenylaminomethylene)-2H,3H,4H-pyran-2,4-dione[compound represented by the general formula (I) of which A is (b), R³=methyl and R=n-octadecyl]

Title compound was synthesized from 4-hydroxy-6-methyl-2-pyrone and4-n-octadecyloxycarbonyl-N-formanilide using the same reactionconditions and after-treatment used in EXAMPLE 12.

Purified product having the melting point of 137 to 138.5° C. wasobtained through recrystalization from toluene.

Mass spectrum: m/z 525(M++1, 100%), 524(10), 496(17), 482(15), 468(19),454(15), 440(14), 426(14), 412(12), 387(13), 385(10), 384(11), 370(11),356(11), 342(12), 328(12), 275(14), 274(69), 273(68), 257(38), 256(56),230(17), 229(67), 172(15), 165(11), 146(11), 144(18), 138(13), 137(32),120(22), 117(12), 97(12), 91(19);

Ultraviolet absorption spectrum (chloroform): λ max(nm) 372 (ε max30,200).

Example 16

Synthesis of6-methyl-3-[4-(2-ethylhexyloxycarbonylphenyl)-aminomethylene]-2H,3H,4H-pyran-2,4-dione[compound represented by the general formula (I) of which A is (b), R³=methyl and R=2-ethylhexyl]

Title compound was synthesized from 4-hydroxy-6-methyl-2-pyrone and4-(2-etylhexyloxycarbonyl)-N-formanilide using the same reactionconditions and after-treatment used in EXAMPLE 12.

Purified product having the melting point of 173.5 to 174.5° C. wasobtained through recrystalization from toluene.

Mass spectrum: m/z 3850(M++1, 35%), 274(21), 273(100), 256(34), 188(6),172(9), 144(8);

Ultraviolet absorption spectrum (chloroform): λ max(nm) 373 (ε max34,300).

Example 17

Practical examples of formulation of skin ointment according to thepresent invention hereunder will be described.

According to the formulation listed in Table 4, a cosmetic liquidcontaining the compound according to EXAMPLE 16, that is6-methyl-3-[4-(2-ethylhexyloxycarbonylphenyl)-aminomethylene]-2H,3H,4H-pyran-2,4-dioneand as control cosmetic liquids, cosmetic liquids containing compound ofControl 1, that is 2,2',4,4'-tetrahydroxybenzophenone, and compound ofControl 2, that is 2-ethylhexyl p-methoxycinnamate, respectively, wereprepared.

                  TABLE 4                                                         ______________________________________                                        Composition    EXAMPLE 17 Control 1                                                                              Control 2                                  ______________________________________                                        ethanol        8.0        8.0      8.0                                          glycerin 2.0 2.0 2.0                                                          citric acid 0.02 0.02 0.02                                                    sodium citrate 0.1 0.1 0.1                                                    methylparaben 0.05 0.05 0.05                                                  POE hardened caster oil 0.5 0.5 0.5                                           perfume some some some                                                        compound of EXAMPLE 16 1.0 -- --                                              compound of Control 1 --  1.0 --                                              compound of Control 2 -- --  1.0                                              propylene glycol 7.0 7.0 7.0                                                  purified water rest rest rest                                               ______________________________________                                    

Control 1 exhibited pale yellow and was not suitable for cosmeticliquid.

Confirmation of Sunscreening Effect

Cosmetic liquid according to EXAMPLE 17 in which compound producedaccording to EXAMPLE 16 and that of Control 2 were, respectively,applied on the skin and their effect at practical use in beach wastested. On each of right or left half area of the back of ten respectivemale and female, each sample solution was applied, and the degree ofsuntan was examined and obtained results was listed in Table 5. Abovedescribed estimation criteria was used.

                  TABLE 5                                                         ______________________________________                                        Estimation   Area applied with                                                                         Area applied                                           criteria: EXAMPLE 17 with Control 2                                         ______________________________________                                        ∘                                                                              20          12                                                     Δ 0 6                                                                   Δ - × 0 2                                                         × 0 0                                                                   Frequency of No itching 7 cases                                               skin trouble  slight rash 1 case                                            ______________________________________                                    

Example 18

Light Stability Effect for Polymer Materials

Each of 0.05, 0.2 and 0.5 part by weight of sample produced according toEXAMPLE 16 was formulated with 100 parts by weight of polyethylenepowder or polypropylene powder, mixed well using a mixer, then meltedand kneaded using a extruder having the diameter of 25 mm at cylindertemperature of 200° C., and pelletized. Obtained pellets were compactedinto sheets of 0.25 mm thickness at 210° C. to prepare test strips.Obtained test strips were punched into dumbbell shapes accommodating toa tension test. Test strip of control which did not contain lightstabilizing agent was prepared, using the above described same method,and test strips were examined.

Using the WEL-75XS-HS-BEC model xenon sunshine long-life weatherometermanufactured by Suga Shiken-Kiki Co. Ltd., these test strips werelight-irradiated with black panel temperature of 80° C., and wereexamined for lowering in tensile strength over time.

The tension test and calculation of tension strength was performedaccording above described methods.

Obtained results were as listed in Table 6. As apparent from the resultsshown in Table 6, the aminomethylene pyrone derivatives according to thepresent invention show prominent stabilizing effect (that is, elongatedtime to deterioration).

                  TABLE 6                                                         ______________________________________                                                 (unit: kgf)                                                          Name of resin                                                                            200    400     600   800   1000  1200                                 hrs hrs hrs hrs hrs hrs                                                    ______________________________________                                        Polypropylene: no,                                                                       3.15   2.13    0     --    --    --                                  0.05 (wt%) 3.40 3.34 2.98 --  --  --                                          0.2 (wt%) 3.65 3.49 3.23 -- -- --                                             0.5 (wt%) 3.85 3.62 3.42 -- -- --                                             Polyethylene: no, 2.42 2.29 2.25 2.10 1.90 0                                  0.05 (wt%) 2.50 2.47 2.44 2.42 2.23 2.20                                      0.2 (wt%) 2.58 2.50 2.49 2.44 2.37 2.31                                       0.5 (wt%) 2.66 2.59 2.55 2.51 2.41 2.38                                     ______________________________________                                    

Example 19

Synthesis of1,3-dimethyl-5-(4-methoxycarbonylphenyl)-aminomethylene-barbituric acid[compound represented by the general formula (I) of which A is (c), R⁴=R⁵ =methyl and R=methyl]

After stirring suspension containing 0.20 mol of 1,3-dimethyl barbituricacid, 0.50 mol of 4-methoxycarbonyl-N-formanilide and 25 ml of toluene(solvent), 0.50 mol of phosphorus oxychloride is added to the suspensionover 15 minutes. During the addition, temperature is maintained at 45°C. or lower. The suspension is further stirred for 10 minutes, then 250ml of hot solution of toluene containing 0.48 mol of 1,3-dimethylbarbituric acid is added to at 60 to 65° C., over 45 minutes. Thereaction mixture is constantly stirred and allowed to cool to roomtemperature, and reaction is terminated by adding the reaction mixturedropwise into 600 ml of 15% sodium hydroxide solution. Obtained organiclayer is being washed with 200 ml of saturated aqueous solution ofsodium chloride. The organic layer is fractionated, allowed to dry onanhydrous sodium sulfate, filtrated and concentrated to obtain crudeproduct.

Purified product having the melting point of 239.5 to 240.5 t isobtained through recrystalization from ethanol/dioxane.

Ultraviolet absorption spectrum (ethanol): λ max(nm) 352, (ε max49,000).

Example 20

Synthesis of1,3-dimethyl-5-(4-n-propoxycarbonylphenyl)-aminomethylene-barbituricacid [compound represented by the general formula (I) of which A is (c),R⁴ =R⁵ =methyl and R=n-propyl]

Title compound was synthesized from 1,3-dimethyl barbituric acid and4-n-propyloxycarbonyl-N-formanilide using the same reaction conditionsand after-treatment used in EXAMPLE 19.

Purified product having the melting point of 150 to 151° C. was obtainedthrough recrystalization from ethanol/dioxane.

Ultraviolet absorption spectrum (ethanol): λ max(nm) 354 (ε max 48,400).

Example 21

Synthesis of1,3-dimethyl-5-(4-n-butoxycarbonylphenyl)-aminomethylene-barbituric acid[compound represented by the general formula (I) of which A is (c), R⁴=R⁵ =methyl and R=n-butyl]

Title compound was synthesized from 1,3-dimethyl barbituric acid and4-n-butyloxycarbonyl-N-formanilide using the same reaction conditionsand after-treatment used in EXAMPLE 19.

Purified product having the melting point of 139 to 140° C. was obtainedthrough recrystalization from ethanol/dioxane.

Ultraviolet absorption spectrum (ethanol): λ max(nm) 353 (ε max 47,800).

Example 22

Synthesis of1,3-dimethyl-5-(4-n-octadecyloxycarbonyl-phenyl)aminomethylene-barbituricacid [compound represented by the general formula (I) of which A is (c),R⁴ =R⁵ =methyl and R=n-octadecyl]

Title compound was synthesized from 1,3-dimethyl barbituric acid and4-n-octadecyloxycarbonyl-N-formanilide using the same reactionconditions and after-treatment used in EXAMPLE 19.

Purified product having the melting point of 116.5 to 117.5° C. wasobtained through recrystalization from toluene.

Ultraviolet absorption spectrum (chloroform): λ max(nm) 356 (ε max38,800).

Example 23

Synthesis of 1,3-dimethyl-5-{N-[4-(2-ethylhexyl)oxycarbonylphenyl]aminomethylene} barbituric acid[compound represented by the general formula (I) of which A is (c), R⁴=R⁵ =methyl and R=2-ethylhexyl]

Title compound was synthesized from 1,3-dimethyl barbituric acid and4-(2-ethylhexyl)oxycarbonyl-N-formanilide using the same reactionconditions and after-treatment used in EXAMPLE 19.

Purified product having the melting point of 164.5 to 165.5° C. wasobtained through recrystalization from toluene.

Ultraviolet absorption spectrum (ethanol): λ max(nm) 356 (ε max 40,700).

Example 24

Practical examples of formulation of skin ointment according to thepresent invention hereunder will be described.

According to the formulation listed in Table 7, a cosmetic liquidcontaining the compound according to EXAMPLE 23, that is 1,3-dimethyl-5-{N-[4-(2-ethylhexyl)oxycarbonylphenyl]-aminomethylene} barbituric acidand as control cosmetic liquids, cosmetic liquids containing compound ofControl 1, that is 2,2',4,4'-tetrahydroxybenzophenone, and compound ofControl 2, that is 2-ethylhexyl p-methoxycinnamate, respectively, wereprepared.

                  TABLE 71                                                        ______________________________________                                        Composition    EXAMPLE 24 Control 1                                                                              Control 2                                  ______________________________________                                        ethanol        8.0        8.0      8.0                                          glycerin 2.0 2.0 2.0                                                          citric acid 0.02 0.02 0.02                                                    sodium citrate 0.1 0.1 0.1                                                    methylparaben 0.05 0.05 0.05                                                  POE hardened caster oil 0.5 0.5 0.5                                           perfume some some some                                                        compound of EXAMPLE 23 1.0 -- --                                              compound of Control 1 --  1.0 --                                              compound of Control 2 -- --  1.0                                              propylene glycol 7.0 7.0 7.0                                                  purified water rest rest rest                                               ______________________________________                                    

Control 1 exhibited pale yellow and was not suitable for cosmeticliquid.

Confirmation of Sunscreening Effect

Composition prepared in EXAMPLE 23 and cosmetic liquid according toControl 2 were, respectively, applied on the skin and their effect atpractical use in beach was tested. On each of right or left half area ofthe back of ten respective male and female, each sample solution wasapplied, and the degree of suntan was examined and obtained results waslisted in Table 8. Estimation was performed according to above describedestimation criteria.

                  TABLE 8                                                         ______________________________________                                        Estimation   Area applied with                                                                         Area applied with                                      criteria EXAMPLE 24 control 2                                               ______________________________________                                        ∘                                                                              18          12                                                     Δ 2 6                                                                   Δ - × 0 2                                                         × 0 0                                                                   Frequency of No itching 7 cases                                               skin trouble  slight rash 1 case                                            ______________________________________                                    

Example 25

Light Stability Effect for Polymer Materials

Each of 0.05, 0.2 and 0.5 part by weight of sample produced according toEXAMPLE 23 was formulated with 100 parts by weight of polyethylenepowder or polypropylene powder, mixed well using a mixer, then meltedand kneaded using a extruder having the diameter of 25 mm at cylindertemperature of 200° C., and pelletized. Obtained pellets were compactedinto sheets of 0.25 mm thickness at 210° C. to prepare test strips.Obtained test strips were punched into dumbbell shapes accommodating toa tension test. Test strip of control which did not contain lightstabilizing agent was prepared, using the above described same method,and test strips were examined.

Using the WEL-75XS-HS-BEC model xenon sunshine long-life weatherometermanufactured by Suga Shiken-Kiki Co. Ltd., these test strips werelight-irradiated with black panel temperature of 80° C., and wereexamined for lowering in tensile strength over time.

The tension test and calculation of tension strength was performedaccording above described methods.

Obtained results were as listed in Table 9. As apparent from the resultsshown in Table 9, the aminomethylene barbituric acid derivativesaccording to the present invention show prominent stabilizing effect(that is, elongated time to deterioration).

                  TABLE 9                                                         ______________________________________                                                 (unit: kgf)                                                                     200    400     600   800   1000  1200                                Name of risin hrs hrs hrs hrs hrs hrs                                       ______________________________________                                        Polypropylene: no,                                                                       3.15   2.13    0     --    --    --                                  0.05 (wt%) 3.58 3.07 2.91 -- -- --                                            0.2 (wt%) 3.72 3.46 3.38 -- -- --                                             0.5 (wt%) 3.98 3.82 2.64 -- -- --                                             Polyethylene: no, 2.42 2.29 2.25 2.10 1.90 0                                  0.05 (wt%) 2.68 2.58 2.50 2.48 2.32 2.22                                      0.2 (wt%) 2.83 2.70 2.62 2.38 2.42 2.38                                       0.5 (wt%) 2.88 2.80 2.76 2.70 2.64 2.60                                     ______________________________________                                    

Example 26

Synthesis of3-[4-(2-ethylhexyloxycarbonyl)phenyl-aminomethylene]chroman-2,4-dione[compound represented by the general formula (I) of which A is (d), R⁶=hydrogen atom, n=1 and R=2-ethylhexyl]

After stirring suspension containing 0.20 mol of 4-hydroxy coumarin,0.50 mol of 4-(2-ethylhexyloxycarbonyl)-N-formanilide and 25 ml oftoluene, 0.50 mol of phosphorus oxychloride is added to the suspensionover 15 minutes. During the addition, temperature is maintained at 45°C. or lower. The suspension is further stirred for 10 minutes, then 250ml of hot solution of toluene containing 0.48 mol of 4-hydroxy coumarinis added to at 60 to 65° C., over 45 minutes. The reaction mixture isconstantly stirred and allowed to cool to room temperature, and reactionis terminated by adding the reaction mixture dropwise into 600 ml of 15%sodium hydroxide solution. Obtained organic layer is being washed with200 ml of saturated aqueous solution of sodium chloride. The organiclayer is fractionated, allowed to dry on anhydrous sodium sulfate,filtrated and concentrated to obtain crude product.

Purified product having the melting point of 179 to 180° C. is obtainedthrough recrystalization from dioxane.

Ultraviolet absorption spectrum (chloroform): λ max(nm) 375 (ε max38,500);

Infrared absorption spectrum: cm⁻¹ (KBr) 3420 (NH), 1708 (ester andlactone C═O), 1642 (4-position C═O ), 1630 (--NH--CH═C═), 1280(C--O--C).

Example 27

Synthesis of 3-(4-ethoxycarbonylphenylaminomethylene)chroman-2,4-dione[compound represented by the general formula (I) of which A is (d), R⁶=hydrogen atom, n=1 and R=ethyl]

Same procedure used in EXAMPLE 26, except that4-ethoxycarbonyl-N-formanilide was used instead of4-(2-ethylhexyloxycarbonyl)-N-formanilide, was repeated.

Melting point: 233 to 234° C.;

Ultraviolet absorption spectrum (chloroform): λ max(nm) 374, (ε max38,200);

Infrared absorption spectrum: cm⁻¹ (KBr) 3430 (NH), 1718 (ester andlactone C═O ), 1650 (4-position C═O ), 1638 (--NH--CH═C═), 1278(C--O--C).

Example 28

Synthesis of 3-(4-n-propoxycarbonylphenylaminomethylene)chroman-2,4-dione [compound represented by the general formula(I) of which A is (d), R⁶ =hydrogen atom, n=1 and R=n-propyl]

Same procedure used in EXAMPLE 26, except that4-n-propoxycarbonyl-N-formanilide was used instead of4-(2-ethylhexyloxycarbonyl)-N-formanilide, was repeated.

Melting point: 211.5 to 212.5° C.

Ultraviolet absorption spectrum (chloroform): λ max(nm) 375 (ε max37,600);

Infrared absorption spectrum: cm⁻¹ (KBr) 3430 (NH), 1718 (ester andlactone C═O ), 1650 (4-position C═O ), 1630 (--NH--CH═C═), 1278(C--O--C).

Example 29

Synthesis of3-(4-isopropoxycarbonylphenylaminomethylene)chroman-2,4-dione [compoundrepresented by the general formula (I) of which A is (d), R⁶ =hydrogenatom, n=1 and R=isopropyl]

Same procedure used in EXAMPLE 26, except that4-isopropoxycarbonyl-N-formanilide was used instead of4-(2-ethylhexyloxycarbonyl)-N-formanilide, was repeated.

Melting point: 206.5 to 207° C.;

Ultraviolet absorption spectrum (chloroform): λ max(nm) 374 (ε max35,600);

Infrared absorption spectrum: cm⁻¹ (KBr) 3430 (NH), 1710 (ester andlactone C═O ), 1650 (4-position C═O ), 1630 (--NH--CH═C═), 1278(C--O--C).

Example 30

Synthesis of 3-(4-n-butoxycarbonylphenylaminomethylene)chroman-2,4-dione[compound represented by the general formula (I) of which A is (d), R⁶=hydrogen atom, n=1 and R=n-butyl]

Same procedure used in EXAMPLE 26, except that4-n-butoxycarbonyl-N-formanilide was used instead of4-(2-ethylhexyloxycarbonyl)-N-formanilide, was repeated.

Melting point: 207 to 207.5° C.;

Ultraviolet absorption spectrum (chloroform): λ max(nm) 375 (ε max38,400);

Infrared absorption spectrum: cm⁻¹ (KBr) 3430 (NH), 1720 (ester andlactone C═O ), 1650 (4-position C═O ), 1630 (--NH--CH═C═), 1275(C--O--C).

Example 31

Synthesis of3-(4-isobutoxycarbonylphenylaminomethylene)chroman-2,4-dione [compoundrepresented by the general formula (I) of which A is (d), R⁶ =hydrogenatom, n=1 and R=isobutyl]

Same procedure used in EXAMPLE 26, except that4-isobutoxycarbonyl-N-formanilide was used instead of4-(2-ethylhexyloxycarbonyl)-N-formanilide, was repeated.

Melting point: 221.5 to 222.5° C.;

Ultraviolet absorption spectrum (chloroform): λ max(nm) 376 (ε max38,000)

Infrared absorption spectrum: cm⁻¹ (KBr) 3440 (NH), 1718 (ester andlactone C═O ), 1650 (4-position C═O ), 1628 (--NH--CH═C═), 1272(C--O--C).

Example 32

Practical examples of formulation of skin ointment according to thepresent invention hereunder will be described.

According to the formulation listed in Table 10, a cosmetic liquidcontaining the compound according to EXAMPLE 26, that is3-[4-(2-ethylhexyloxycarbonyl)phenylaminomethylene]chroman-2,4-dione andas control cosmetic liquids, cosmetic liquids containing compound ofControl 1, that is 2,2',4,4'-tetrahydroxybenzophenone, and compound ofControl 2, that is 2-ethylhexyl p-methoxycinnamate, respectively, wereprepared.

                  TABLE 10                                                        ______________________________________                                        Composition    EXAMPLE 32 Control 1                                                                              Control 2                                  ______________________________________                                        ethanol        8.0        8.0      8.0                                          glycerin 2.0 2.0 2.0                                                          citric acid 0.02 0.02 0.02                                                    sodium citrate 0.1 0.1 0.1                                                    methylparaben 0.05 0.05 0.05                                                  POE hardened caster oil 0.5 0.5 0.5                                           perfume some some some                                                        compound of EXAMPLE 26 1.0 -- --                                              compound of Control 1 --  1.0 --                                              compound of Control 2 -- --  1.0                                              propylene glycol 7.0 7.0 7.0                                                  purified water rest rest rest                                               ______________________________________                                    

Control 1 exhibited pale yellow and was not suitable for cosmeticliquid.

Example 33

Confirmation of Sunscreening Effect

Cosmetic liquid of the present invention, containing the compoundproduced according to EXAMPLE 30, in stead of compound producedaccording to EXAMPLE 26 which was used in EXAMPLE 32, and cosmeticliquid according to Control 2 were, respectively, applied on the skinand their effect at practical use in beach was tested. On each of rightor left half area of the back of ten respective male and female, eachsample solution was applied, and the degree of suntan was examined andobtained results was listed in Table 11. Estimation was performedaccording to above described estimation criteria.

                  TABLE 11                                                        ______________________________________                                        Estimation   Area applied with                                                                         Area applied with                                      criteria EXAMPLE 33 Control 2                                               ______________________________________                                        ∘                                                                              19          17                                                     Δ 1 2                                                                   Δ - × 0 1                                                         × 0 0                                                                   Frequency of No itching 3 cases                                               skin trouble  slight rash 1 case                                            ______________________________________                                    

Example 34

Light Stability Effect for Polymer Materials

Each of 0.05, 0.2 and 0.5 part by weight of sample produced according toEXAMPLE 26 was formulated with 100 parts by weight of polyethylenepowder or polypropylene powder, mixed well using a mixer, then meltedand kneaded using a extruder having the diameter of 25 mm at cylindertemperature of 200° C., and pelletized. Obtained pellets were compactedinto sheets of 0.25 mm thickness at 210° C., to prepare test strips.Obtained test strips were punched into dumbbell shapes accommodating toa tension test. Test strip of control which did not contain lightstabilizing agent was prepared, using the above described same method,and test strips were examined.

Using the WEL-75XS-HS-BEC model xenon sunshine long-life weatherometermanufactured by Suga Shiken-Kiki Co. Ltd., these test strips werelight-irradiated with black panel temperature of 80° C., and wereexamined for lowering in tensile strength over time.

The tension test and calculation of tension strength was performedaccording above described methods.

Obtained results were as listed in Table 12. As apparent from theresults shown in Table 12, the aminomethylene chroman derivativesaccording to the present invention show prominent stabilizing effect(that is, elongated time to deterioration).

                  TABLE 12                                                        ______________________________________                                                 (unit: kgf)                                                                     200    400     600   800   1000  1200                                Name of resin hrs hrs hrs hrs hrs hrs                                       ______________________________________                                        Polypropylene: no,                                                                       3.15   2.13    0     --    --    --                                  0.05 (wt%) 3.56 3.04 2.90 -- -- --                                            0.2 (wt%) 3.70 3.40 3.36 -- -- --                                             0.5 (wt%) 3.92 3.81 3.60 -- -- --                                             Polyethylene: no, 2.42 2.26 2.25 2.10 1.90 0                                  0.05 (wt%) 2.82 2.72 2.60 2.63 2.50 2.40                                      0.2 (wt%) 2.80 2.92 2.80 2.74 258 2.60                                        0.5 (wt%) 3.02 3.02 2.92 2.80 2.70 2.80                                     ______________________________________                                    

Example 35

Synthesis of2,2-dimethyl-5-[4-(2-ethylhexyloxycarbonyl)phenylaminomethylene]-1,3-dioxane-4,6-dione[compound represented by the general formula (I) of which A is (e), R⁷=R⁸ =methyl and R=2-ethylhexyl]

After stirring suspension containing 0.20 mol of Meldrum's acid, 0.50mol of 4-(2-ethylhexyloxycarbonyl)-N-formanilide and 25 ml of toluene,0.50 mol of phosphorus oxychloride is added to the suspension over 15minutes. During the addition, temperature is maintained at 45° C. orlower. The suspension is further stirred for 10 minutes, then 250 ml ofhot solution of toluene containing 0.30 mol of Meldrum's acid is addedto at 60 to 65° C., over 45 minutes. The reaction mixture is constantlystirred and allowed to cool to room temperature, and reaction isterminated by adding the reaction mixture dropwise into 600 ml of 15%sodium hydroxide solution. Obtained organic layer is being washed with200 ml of saturated aqueous solution of sodium chloride. The organiclayer is fractionated, allowed to dry on anhydrous sodium sulfate,filtrated and concentrated to obtain crude product.

Purified product having the melting point of 148.5 to 149.5° C. isobtained through recrystalization from dioxane.

Ultraviolet absorption spectrum (chloroform): λ max(nm) 339,

ε max 35,500;

Infrared absorption spectrum (chloroform): cm⁻¹ (KBr) 3420(NH), 1708(ester and lactone C═O ), 1642 (4-position C═O ), 1630 (--NH--CH═C═),1280 (C--O--C).

Example 36

Synthesis of2,2-dimethyl-5-(4-ethoxycarbonylphenylaminomethylene)-1,3-dioxane-4,6-dione[compound represented by the general formula (I) of which A is (e), R⁷=R⁸ =methyl and R=ethyl]

Same procedure used in EXAMPLE 35, except that4-ethoxycarbonyl-N-formanilide was used instead of4-(2-ethylhexyloxycarbonyl)-N-formanilide, was repeated.

Melting point: 184 to 184.5° C.;

Ultraviolet absorption spectrum (chloroform): λ max (nm) 338,

ε max 35,700;

Infrared absorption spectrum: cm⁻¹ (KBr) 3220 (NH), 1730 (lactone C═O ),1718 (ester C═O ), 1688 (4-position C═O ), 1652 (--NH--CH═C═).

Example 37

Synthesis of2,2-dimethyl-5-(4-n-propoxycarbonylphenylaminomethylene)-1,3-dioxane-4,6-dione[compound represented by the general formula (I) of which A is (e), R⁷=R⁸ =methyl and R=n-propyl]

Same procedure used in EXAMPLE 35, except that4-(n-proxycarbonyl)-N-formanilide was used instead of4-(2-ethylhexyloxycarbonyl)-N-formanilide, was repeated.

Melting point: 154 to 155° C.;

Ultraviolet absorption spectrum (chloroform): λ max (nm) 337,

ε max max 35,900;

Infrared absorption spectrum: cm⁻¹ (KBr) 3229 (NH), 1732 (lactone C═O ),1718 (ester C═O ), 1682 (4-position C═O ), 1638 (--NH--CH═C═).

Example 38

Synthesis of2,2-dimethyl-5-(4-isopropoxycarbonylphenylaminomethylene)-1,3-dioxane-4,6-dione[compound represented by the general formula (I) of which A is (e), R⁷=R⁸ =isopropyl and R=isopropyl]

Same procedure used in EXAMPLE 35, except that4-(isoproxycarbonyl)-N-formanilide was used instead of4-(2-ethylhexyloxycarbonyl)-N-formanilide, was repeated.

Melting point: 185 to 186° C.;

Ultraviolet absorption spectrum (chloroform): λ max(nm) 338,

ε max 35,200;

Infrared absorption spectrum: cm⁻¹ (KBr) 3220 (NH), 1736 (lactone C═O ),1718 (ester C═O ), 1682 (4-position C═O ), 1640 (--NH--CH═C═).

Example 39

Synthesis of2,2-dimethyl-5-(4-n-butoxycarbonylphenylaminomethylene)-1,3-dioxane-4,6-dione[compound represented by the general formula (I) of which A is (e), R⁷=R⁸ =methyl and R=n-butyl]

Same procedure used in EXAMPLE 35, except that4-(n-butoxycarbonyl)-N-formanilide was used instead of4-(2-ethylhexyloxycarbonyl)-N-formanilide, was repeated.

Melting point: 161 to 162° C.;

Ultraviolet absorption spectrum (chloroform): λ max(nm) 338,

ε max 35,200;

Infrared absorption spectrum: cm⁻¹ (KBr) 3220 (NH), 1738 (lactone C═O ),1716 (ester C═O ), 1680 (4-position C═O ), 1630 (--NH--CH═C═).

Example 40

Synthesis of2,2-dimethyl-5-(4-isobutoxycarbonylphenylaminomethylene)-1,3-dioxane-4,6-dione[compound represented by the general formula (I) of which A is (e), R⁷=R⁸ =methyl and R=isobutyl]

Same procedure used in EXAMPLE 35, except that4-(isobutoxycarbonyl)-N-formanilide was used instead of4-(2-ethylhexyloxycarbonyl)-N-formanilide, was repeated.

Melting point: 186.5 to 187.5° C.;

Ultraviolet absorption spectrum (chloroform): λ max(nm) 338,

ε max 43,400;

Infrared absorption spectrum: cm⁻¹ (KBr) 3220 (NH), 1732 (lactone C═O ),1705 (ester C═O ), 1680 (4-position C═O ), 1632 (--NH--CH═C═).

Example 41

Practical examples of formulation of skin ointment according to thepresent invention hereunder will be described.

According to the formulation listed in Table 13, a cosmetic liquidcontaining the compound according to EXAMPLE 35, that is2,2-dimethyl-5-[4-(2-ethylhexyloxycarbonyl)phenylaminomethylene]-1,3-dioxane-4,6-dioneand as control cosmetic liquids, cosmetic liquids containing compound ofControl 1, that is 2,2',4,4'-tetrahydroxybenzophenone, and compound ofControl 2, that is 2-ethylhexyl p-methoxycinnamate, respectively, wereprepared.

                  TABLE 13                                                        ______________________________________                                        Composition    EXAMPLE 41 Control 1                                                                              Control 2                                  ______________________________________                                        ethanol        8.0        8.0      8.0                                          glycerin 2.0 2.0 2.0                                                          citric acid 0.02 0.02 0.02                                                    sodium citrate 0.1 0.1 0.1                                                    methylparaben 0.05 0.05 0.05                                                  POE hardened caster oil 0.5 0.5 0.5                                           perfume some some some                                                        compound of EXAMPLE 35 1.0 -- --                                              compound of Control 1 --  1.0 --                                              compound of Control 2 -- --  1.0                                              propylene glycol 7.0 7.0 7.0                                                  purified water rest rest rest                                               ______________________________________                                    

Control 1 exhibited pale yellow and was not suitable for cosmeticliquid.

Example 42

Confirmation of Sunscreening Effect

Cosmetic liquid of the present invention, containing the compoundproduced according to EXAMPLE 39, in stead of compound producedaccording to EXAMPLE 35 which was used in EXAMPLE 41, and cosmeticliquid according to Control 2 were, respectively, applied on the skinand their effect at practical use in beach was tested. On each of rightor left half area of the back of ten respective male and female, eachsample solution was applied, and the degree of suntan was examined andobtained results was listed in Table 14. Estimation was performedaccording to above described estimation criteria.

                  TABLE 14                                                        ______________________________________                                        Estimation   Area applied with                                                                         Area applied with                                      criteria EXAMPLE 41 Control 2                                               ______________________________________                                        ∘                                                                              18          17                                                     Δ 1 2                                                                   Δ - × 1 1                                                         × 0 0                                                                   Frequency of itching 1 case itching 3 cases                                   skin trouble  slight rash 1 case                                            ______________________________________                                    

Example 43

Light Stability Effect for Polymer Materials

Each of 0.05, 0.2 and 0.5 part by weight of sample produced according toEXAMPLE 35 was formulated with 100 parts by weight of polyethylenepowder or polypropylene powder, mixed well using a mixer, then meltedand kneaded using a extruder having the diameter of 25 mm at cylindertemperature of 200° C., and pelletized. Obtained pellets were compactedinto sheets of 0.25 mm thickness at 210° C. to prepare test strips.Obtained test strips were punched into dumbbell shapes accommodating toa tension test. Test strip of control which did not contain lightstabilizing agent was prepared, using the above described same method,and test strips were examined.

Using the WEL-75XS-HS-BEC model xenon sunshine long-life weatherometermanufactured by Suga Shiken-Kiki Co.Ltd., these test strips werelight-irradiated with black panel temperature of 80° C., and wereexamined for lowering in tensile strength over time.

The tension test and calculation of tension strength was performedaccording above described methods.

Obtained results were as listed in Table 15. As apparent from theresults shown in Table 15, the aminomethylene chroman derivativesaccording to the present invention show prominent stabilizing effect(that is, elongated time to deterioration).

                  TABLE 15                                                        ______________________________________                                                 (unit: kgf)                                                                     200    400     600   800   1000  1200                                Name of resin hrs hrs hrs hrs hrs hrs                                       ______________________________________                                        Polypropylene: no,                                                                       3.15   2.13    0     --    --    --                                  0.05 (wt%) 3.68 3.17 3.01 -- -- --                                            0.2 (wt%) 3.76 3.44 3.36 -- -- --                                             0.5 (wt%) 3.96 3.80 3.62 -- -- --                                             Polyethylene: no, 2.42 2.29 2.25 2.10 1.90 0                                  0.05 (wt%) 2.86 2.76 2.68 2.66 2.50 2.21                                      0.2 (wt%) 2.81 2.88 2.80 2.76 2.60 2.39                                       0.5 (wt%) 3.06 2.98 2.94 2.88 2,82 2.78                                     ______________________________________                                    

What is claimed is:
 1. An aminomethylene derivative represented bygeneral formula (I): ##STR19## wherein A is a cyclic oxo group offollowing general formula (d): ##STR20## wherein R⁶ is a group selectedfrom the group consisting of linear or branched, saturated orunsaturated alkyl groups, cycloalkyl groups, aralkyl groups, arylgroups, alkoxy groups, alkoxycarbonyl groups, acyl groups, dialkylaminogroups and halogens, and R is a group selected from the group consistingof linear or branched, saturated or unsaturated alkyl groups, aralkylgroups, aryl groups, cycloalkyl groups and alkoxycarbonylalkylenegroups, and n is an integer of 0 to 4 wherein when n is 2 or more, eachof plural R⁶ s can be different groups within the above-describedgroups.
 2. A method for producing an aminomethylene derivativerepresented by general formula (I): ##STR21## wherein A is followinggeneral formula (d): ##STR22## wherein R⁶ is a group selected from thegroup consisting of linear or branched, saturated or unsaturated alkylgroups, cycloalkyl groups, aralkyl groups, aryl groups, alkoxy groups,alkoxycarbonyl groups, acyl groups, dialkylamino groups and halogens,and R is a group selected from the group consisting of linear orbranched, saturated or unsaturated alkyl groups, aralkyl groups, arylgroups, cycloalkyl groups and alkoxycarbonylalkylene groups, and n is aninteger of 0 to 4 wherein when n is 2 or more, each of plural R⁶ s canbe different groups within the above-described groups,wherein a cyclicoxo compound represented by general formula (II):

    A'                                                         (II)

wherein A' is a compound of following general formula (d): ##STR23##wherein R⁶ is a group selected from the group consisting of linear orbranched, saturated or unsaturated alkyl groups, cycloalkyl groups,aralkyl groups, aryl groups, alkoxy groups, alkoxycarbonyl groups, acylgroups, dialkylamino groups and halogens, and n is an integer of 0 to 4wherein when n is 2 or more, each of plural R⁶ s can be different groupswithin the above-described groups, is allowed to react with anN-formylaminobenzoate derivative represented by general formula (III):##STR24## wherein R is a group selected from the group consisting oflinear or branched, saturated or unsaturated alkyl groups, cycloalkylgroups, aralkyl groups, aryl groups and alkoxycarbonylalkylene groups,in an organic solvent and in the presence of a halide.
 3. A methodaccording to claim 2, wherein said halide is a chloride.